Composite, electrochemical active material composite using the composite, electrode including the composite or electrochemical active material composite, lithium battery

ABSTRACT

A composite including: at least one selected from a silicon oxide of the formula SiO2 and a silicon oxide of the formula SiOx wherein 0&lt;x&lt;2; and graphene, wherein the silicon oxide is disposed in a graphene matrix.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No.14/733,028 filed on Jun. 8, 2015 in the United States Patent andTrademark Office, which claims priority to and the benefit of KoreanPatent Application No. 10-2014-0070267, filed on Jun. 10, 2014, in theKorean Intellectual Property Office, and all the benefits accruingtherefrom under 35 U.S.C. § 119, the contents of which applications areincorporated herein in their entireties by reference.

BACKGROUND 1. Field

The present disclosure relates to composite, an electrochemically activematerial composite including the composite, an electrode including thecomposite or the electrochemically active material composite, and alithium battery, field emission device, biosensor, semiconductor device,and thermoelectric device that include the composite.

2. Description of the Related Art

Lithium ion batteries have been widely used as power sources for variousportable electronic devices due to their high energy density and ease ofdesign. With the recent greater use of lithium ion batteries as powersources for electric vehicles, power storage, and portable electronicdevices, research into materials that provide higher-energy density andlonger lifetime has increased. In particular, surface coating ofelectrode active materials may be one of the satisfactory ways toimprove the performance of lithium ion batteries with known electrodeactive materials.

Various coating materials are known to improve the performance ofbatteries. However, such known coating materials do not providesatisfactory suppression of a side reaction between an electrode activematerial and an electrolyte, adhesion between an electrode activematerial and a coating material, and electrode conductivity. Thereforethe remains a need for improved electrochemical materials.

SUMMARY

Provided is a composite.

Provided is a method of preparing the composite.

Provided is an electrochemically active material composite including anyof the composite and an electrochemically active material.

Provided is an electrode that includes the composite, or theelectrochemically active material composite including any of thecomposite and an electrochemically active material.

Provided is a lithium battery including the electrode.

Provided is a device including any of the composite.

Additional aspects will be set forth in part in the description whichfollows and, in part, will be apparent from the description.

According to an aspect, a composite includes at least one selected froma silicon oxide of the formula SiO₂ and a silicon oxide of the formulaSiO_(x) wherein 0<x<2; and graphene, wherein the silicon oxide isdisposed in a graphene matrix including the graphene.

According to another aspect, disclosed is a method of preparing acomposite, the method including:

contacting a reaction gas including a carbon source gas and a siliconoxide of the formula SiO_(x) wherein 0<x≤2; and

thermally treating the reaction gas-contacted silicon oxide to preparethe composite.

According to another aspect, an electrochemically active materialcomposite includes the composite and an electrochemically activematerial.

According to another aspect, an electrode includes the composite, or anelectrochemically active material composite including the composite andan electrochemically active material.

According to another aspect, a lithium battery includes the electrode.

According to another aspect, a field emission device includes thecomposite.

According to another aspect, a biosensor includes the composite.

According to another aspect, a semiconductor device includes thecomposite.

According to another aspect, a thermoelectric device includes thecomposite.

BRIEF DESCRIPTION OF THE DRAWINGS

These and/or other aspects will become apparent and more readilyappreciated from the following description of the embodiments, taken inconjunction with the accompanying drawings in which:

FIG. 1 is a schematic view of an embodiment of a method of preparing acomposite;

FIG. 2 is a graph of temperature (degrees Celsius, ° C.) versus time(minutes, min) for a method of forming graphene by vapor deposition in amethod of preparing a composite;

FIG. 3A is a schematic view of an embodiment of a lithium battery;

FIG. 3B is a schematic view of an embodiment of a thermoelectric module;

FIG. 3C illustrates an embodiment of thermoelectric cooling using thePeltier effect;

FIG. 3D illustrates an embodiment of thermoelectric power generationusing the Seebeck effect;

FIG. 3E is a schematic cross-sectional view illustrating an embodimentof a structure of an electrode of a biosensor;

FIGS. 4A and 4B are high resolution-transmission electron (HR-TEM)images of a composite of Preparation Example 3;

FIGS. 4C and 4D are scanning electron microscopic (SEM) images of thecomposite of Preparation Example 3;

FIGS. 4E and 4F are HR-TEM and SEM images of the composite ofPreparation Example 5, respectively;

FIGS. 4G and 4H are HR-TEM and SEM images of silicon oxide (SiO₂),respectively;

FIGS. 5A to 5F are SEM and HR-TEM images of an electrode material ofExample 1;

FIGS. 5G and 5H are SEM and HR-TEM images, respectively, of a lithiumcomposite oxide of the formula LiNi_(0.5)Co_(0.2)Mn_(0.3)O₂ (NCM) forcomparison with the electrode material of Example 1;

FIGS. 51 to 5K are HR-TEM images of an electrode material of Example 6,and FIGS. 5L and 5M are HR-TEM images of silicon oxide used as astarting material to prepare the electrode material of Example 6;

FIGS. 6A and 6B are graphs of specific capacity (milliampere hours pergram, mAh/g) at a cut-off voltage of 4.4 (volts, V) and 4.5 V,respectively, with respect to cycle number (cycles) for the coin cellsof Manufacture Example 1 and Comparative Manufacture Example 2, obtainedas a result of charge-discharge characteristics evaluation;

FIGS. 6C and 6D are graphs of specific capacity (mAh/g) at a cut-offvoltage of 4.4V and 4.5V, respectively, with respect to the number ofcycles in coin cells of Manufacture Example 5 and ComparativeManufacture Example 3, obtained as a result of charge-dischargecharacteristics evaluation;

FIG. 6E is a graph of specific capacity (mAh/g) with respect to cyclenumber (cycles) for the coin cells of Manufacture Example 6 andComparative Manufacture Examples 4 and 5, obtained as a result ofcharge-discharge characteristics evaluation;

FIG. 6F is a graph of specific capacity (mAh/g) with respect to C ratefor the coin cells of Manufacture Example 1 and Comparative ManufactureExample 2, obtained as a result of rate characteristics evaluation;

FIG. 6G is a graph of specific capacity (mAh/g) with respect to C ratein the coin cells of Manufacture Example 5 and Comparative ManufactureExample 3, obtained as a result of rate characteristics and capacityevaluation;

FIG. 7A is a graph of intensity (arbitrary units, a.u.) versus bindingenergy (electron volts, eV) illustrating the results of X-rayphotoelectron spectroscopy (XPS) analysis on a composite of PreparationExample 4 and an electrode material of Example 4;

FIGS. 7B to 7E illustrate the results of XPS analysis on composites ofPreparation Examples 1, 3 and 5, and structures of ComparativePreparation Examples 2 and 3 in which FIG. 7B is a graph of intensity(counts per second, C/S) versus binding energy (eV), and FIGS. 7C and 7Dare each a graph of intensity (a.u.) versus binding energy (eV);

FIG. 7F is a graph of intensity (a.u.) versus binding energy (eV) whichillustrates XPS valence band spectra of the composites of PreparationExamples 1, 3 and 5, the structures of Comparative Preparation Examples2 and 3;

FIGS. 7G and 7H are each a graph of intensity (a.u.) versus bindingenergy (eV) which illustrate results of compositional XPS analysis onthe composite of Preparation Example 3 and the electrode material ofExample 5, respectively;

FIGS. 8A to 8D illustrate results of scanning electron microscopy withenergy dispersive analysis of X-rays (SEM-EDAX) on the electrodematerial of Example 1 in which FIG. 8A is a secondary electron image ofthe electrode material of Example 1, FIG. 8B is an energy dispersiveX-ray analysis (EDAX) map for Ni of the electrode material Example 1,FIG. 8C is an EDAX map for carbon of the electrode material of Example1, FIG. 8D is an EDAX map for silicon of the electrode material ofExample 1,

FIG. 8E to 8H illustrate the results of scanning electron microscopywith energy dispersive analysis of X-rays (SEM-EDAX) on the electrodematerial of a lithium composite oxide of the formulaLiNi_(0.5)Co_(0.2)Mn_(0.3)O₂ used for preparing the electrode materialof Example 1 in which FIG. 8E is a secondary electron image of thelithium composite oxide LiNi_(0.5)Co_(0.2)Mn_(0.3)O₂, FIG. 8F is asecondary electron image for Ni of the lithium composite oxideLiNi_(0.5)Co_(0.2)Mn_(0.3)O₂, FIG. 8G is an EDAX map for carbon of thelithium composite oxide LiNi_(0.5)Co_(0.2)Mn_(0.3)O₂, and FIG. 8H is anEDAX map for silicon of lithium composite oxideLiNi_(0.5)Co_(0.2)Mn_(0.3)O₂;

FIG. 9A is graph of weight loss (percent, %) versus temperature (° C.)showing the results of thermogravimetric analysis (TGA) of thecomposites of Preparation Examples 1 to 4 and the structure ofComparative Preparation Example 1;

FIG. 9B is a graph of weight loss (percent, %) versus temperature (° C.)showing the results of TGA of the electrode material of Example 1 andNCM;

FIG. 10A is a graph of intensity (a.u.) versus diffraction angle(degrees two-theta, ° 2θ) which illustrates results of X-ray diffractionanalysis on the composites of Preparation Examples 1 and 4 and thestructure of Comparative Preparation Example 1;

FIG. 10B is a graph of intensity (a.u.) versus diffraction angle(degrees two-theta, ° 2θ) which illustrates results of X-ray diffractionanalysis on the composites of Preparation Examples 1, 3 and 5 and thestructures of Comparative Preparation Examples 2 and 3;

FIGS. 11A to 11D are graphs of intensity (a.u.) versus Raman shift(wavenumbers, cm⁻¹) showing Raman spectra of the composites ofPreparation Examples 1 to 4, the structures of Comparative PreparationExamples 2 and 3, and the electrodes materials of Examples 4 and 5;

FIG. 12 is a graph of intensity (a.u.) versus ²⁹Si chemical shift (partsper million, ppm from tetramethylsilane (TMS)) which illustrates resultsof ²⁹Si{¹H}-cross-polarization/magic angle spinning nuclear magneticresonance (²⁹Si{¹H}-CP/MAS NMR) spectroscopy on the composite ofPreparation Example 5, the structure of Comparative Preparation Example2, and SiO₂;

FIGS. 13A to 13F are results of transmission electron withenergy-dispersive X-ray spectrometry (TEM-EDS) analysis on the compositeof Preparation Example 6 in which FIG. 13A is a scanning transmissionelectron (STEM) image, FIG. 13B is a C EDS map, FIG. 13C is a Si and CEDS map, FIG. 13D is a Si EDS map, FIG. 13E is a 0 EDS map, and FIG. 13Fis an O and Si EDS map;

FIGS. 13G to 13K are results of TEM-EDS on silicon oxide (SiO₂) in whichFIG. 13G is a STEM image, FIG. 13H is a C EDS map, FIG. 13I is a Si EDSmap, FIG. 13J is an O EDS map, and FIG. 13K is an O and Si EDS map;

FIGS. 14A to 14D are TEM images of the composite of Preparation Example1;

FIGS. 15A to 15C are results of TEM-EDS analysis on the composite ofPreparation Example 1 in which FIG. 13A is a STEM image, FIG. 15B is aSi EDS map, and FIG. 15C is a graph of intensity (a.u.) versus energy(electron volts, eV); and

FIG. 16 is a result of TEM-EDS analysis on the composite of PreparationExample 3.

DETAILED DESCRIPTION

Reference will now be made in detail to embodiments, examples of whichare illustrated in the accompanying drawings, wherein like referencenumerals refer to like elements throughout. In this regard, the presentembodiments may have different forms and should not be construed asbeing limited to the descriptions set forth herein. Accordingly, theembodiments are merely described below, by referring to the figures, toexplain aspects of the present description. As used herein, the term“and/or” includes any and all combinations of one or more of theassociated listed. “Or” means “and/or.” Expressions such as “at leastone of,” when preceding a list of elements, modify the entire list ofelements and do not modify the individual elements of the list.

It will be understood that when an element is referred to as being “on”another element, it can be directly on the other element or interveningelements may be present therebetween. In contrast, when an element isreferred to as being “directly on” another element, there are nointervening elements present.

It will be understood that, although the terms “first,” “second,”“third” etc. may be used herein to describe various elements,components, regions, layers and/or sections, these elements, components,regions, layers and/or sections should not be limited by these terms.These terms are only used to distinguish one element, component, region,layer or section from another element, component, region, layer orsection. Thus, “a first element,” “component,” “region,” “layer” or“section” discussed below could be termed a second element, component,region, layer or section without departing from the teachings herein.

The terminology used herein is for the purpose of describing particularembodiments only and is not intended to be limiting. As used herein, thesingular forms “a,” “an,” and “the” are intended to include the pluralforms, including “at least one,” unless the content clearly indicatesotherwise. It will be further understood that the terms “comprises”and/or “comprising,” or “includes” and/or “including” when used in thisspecification, specify the presence of stated features, regions,integers, steps, operations, elements, and/or components, but do notpreclude the presence or addition of one or more other features,regions, integers, steps, operations, elements, components, and/orgroups thereof.

Spatially relative terms, such as “beneath,” “below,” “lower,” “above,”“upper” and the like, may be used herein for ease of description todescribe one element or feature's relationship to another element(s) orfeature(s) as illustrated in the figures. It will be understood that thespatially relative terms are intended to encompass differentorientations of the device in use or operation in addition to theorientation depicted in the figures. For example, if the device in thefigures is turned over, elements described as “below” or “beneath” otherelements or features would then be oriented “above” the other elementsor features. Thus, the exemplary term “below” can encompass both anorientation of above and below. The device may be otherwise oriented(rotated 90 degrees or at other orientations) and the spatially relativedescriptors used herein interpreted accordingly.

“About” or “approximately” as used herein is inclusive of the statedvalue and means within an acceptable range of deviation for theparticular value as determined by one of ordinary skill in the art,considering the measurement in question and the error associated withmeasurement of the particular quantity (i.e., the limitations of themeasurement system). For example, “about” can mean within one or morestandard deviations, or within ±30%, 20%, 10%, 5% of the stated value.

Unless otherwise defined, all terms (including technical and scientificterms) used herein have the same meaning as commonly understood by oneof ordinary skill in the art to which this disclosure belongs. It willbe further understood that terms, such as those defined in commonly useddictionaries, should be interpreted as having a meaning that isconsistent with their meaning in the context of the relevant art and thepresent disclosure, and will not be interpreted in an idealized oroverly formal sense unless expressly so defined herein.

Exemplary embodiments are described herein with reference to crosssection illustrations that are schematic illustrations of idealizedembodiments. As such, variations from the shapes of the illustrations asa result, for example, of manufacturing techniques and/or tolerances,are to be expected. Thus, embodiments described herein should not beconstrued as limited to the particular shapes of regions as illustratedherein but are to include deviations in shapes that result, for example,from manufacturing. For example, a region illustrated or described asflat may, typically, have rough and/or nonlinear features. Moreover,sharp angles that are illustrated may be rounded. Thus, the regionsillustrated in the figures are schematic in nature and their shapes arenot intended to illustrate the precise shape of a region and are notintended to limit the scope of the present claims.

“Alkyl” as used herein means a straight or branched chain, saturated,monovalent hydrocarbon group (e.g., methyl or hexyl).

“Alkenyl” means a straight or branched chain, monovalent hydrocarbongroup having at least one carbon-carbon double bond (e.g., ethenyl(—HC═CH₂)).

“Alkynyl” means a straight or branched chain, monovalent hydrocarbongroup having at least one carbon-carbon triple bond (e.g., ethynyl).

“Rare earth” means the fifteen lanthanide elements, i.e., atomic numbers57 to 71, plus scandium and yttrium.

The “lanthanide elements” means the chemical elements with atomicnumbers 57 to 71.

A C rate means a current which will discharge a battery in one hour,e.g., a C rate for a battery having a discharge capacity of 1.6ampere-hours would be 1.6 amperes.

Hereinafter, composites according to embodiments of the presentdisclosure, methods of preparing the same, electrochemically activematerial composites using the composites, lithium batteries includingthe composites or electrochemically active material composites, andfield emission devices, electroluminescent devices, biosensors,semiconductor devices, and thermoelectric devices that use any of thecomposites according to embodiments of the present disclosure will bedescribed in greater detail with reference to the appended drawings.

According to an aspect of the present disclosure, a composite includes:at least one selected from a silicon oxide of the formula SiO₂ and asilicon oxide of the formula SiO_(x) wherein 0<x<2; and graphene,wherein the silicon oxide is disposed in, e.g., embedded in, a graphenematrix comprising the graphene. In an embodiment, the silicon oxide isof the formula SiO_(x) wherein 0<x<2 and is a reduction product of SiO₂.In an embodiment, 0<x<1.9, 0.1<x<0.8, 0.2<x<1.7, 0.3<x<1.6, 0.4<x<1.5,or 0.5<x<1.4. In a preferred embodiment, 1<x<1.9.

As used herein, the term “embedded” may refer to a structure in whichthe silicon oxide (SiO₂) is surrounded by the graphene and may also beconstrued as a structure in which at least part of the silicon oxide isexposed from the graphene matrix.

The graphene may have a branched structure comprising contacting and/orinterconnected graphene particles to provide a branched structure thatresembles the branches of a bush, and the silicon oxide may bedistributed in the graphene having the branched structure.

The graphene may have a globular or spherical structure having a size ofabout 50 nanometers (nm) to about 300 nm, about 75 nm to about 275 nm,or about 100 nm to about 150 nm. As used herein, the term “globular” mayrefer to a substantially spherical shape or any shape similar to sphere,including, for example an ellipse, or the like.

When the globular structure is a sphere, the size of the globularstructure may be an average particle diameter of the sphere. When theglobular structure is an ellipse, the size of the globular structure maybe a major axis diameter of the ellipse.

The silicon oxide may have an average particle diameter of about 1 nm toabout 20 nm, and in some embodiments, about 10 nm to about 20 nm, orabout 5 nm to about 15 nm.

The silicon oxide may be, for example, at least one selected fromSiO_(1.8), SiO_(1.9), SiO_(1.7), SiO_(1.6), SiO_(1.5), and SiO_(1.4),SiO_(1.3).

The graphene may have a degree of crystallinity of about 0.5 to about1.5, for example, about 1.055 to about 1.146, or about 1.06 to about1.14.

The degree of crystallinity (or degree of disordering of graphenecrystals) of the graphene may be obtained by measuring an intensityratio of D peak to G peak (D/G) in a Raman spectra of the composite.

In the composite, the silicon oxide may have a degree of deviation inuniformity of about 1% or less, for example, about 0.0001 to about 1%,about 0.001 to about 0.9%, or about 0.01 to about 0.8%, which may beobtained, for example, by X-ray photoelectron spectroscopy (XPS).

In the composite, a major peak having a Bragg diffraction angle in arange of about 15 degrees two-theta (° 2θ) to about 30° 2θ, about 16° 2θto about 28° 2θ, or about 17° 2θ to about 26° 2θ, and a minor peak in arange of about 40° 2θ to about 50° 2θ, for example, about 40° to about48°, about 42° 2θ to about 46° 2θ, when analyzed using Cu K-alpha X-rayshaving a wavelength of 1.541□.

In some embodiments, the major peak may appear, for example, in a rangeof about 18° to about 28°, and the minor peak may appear, for example,in a range of about 41° to about 46°. As used herein, the major peak mayrefer to a peak having the highest intensity, and the minor peak mayrefer to a peak having a lower intensity than the major peak.

In some embodiments, the major peak may have a full width at halfmaximum (FWHM) of about 5° to about 10°, about 6° to about 9°, or about7° to about 8°. The composite having such X-ray diffractioncharacteristics may have improved characteristics in terms of, forexample, conductivity.

In the composite, there are no silicon dioxide (i.e., SiO₂) and siliconcarbide (SiC) peaks at a chemical shift of about −90 ppm to about −120ppm, versus tetramethylsilane (TMS), when analyzed by²⁹Si{¹H}-cross-polarization magic-angle spinning (CP/MAS) nuclearmagnetic resonance (NMR) spectroscopy.

In some embodiments, the composite may have a clumped structure. Theclumped structure may be, for example, a globular structure. The clumpedstructure may vary depending on the shape of silicon dioxide (SiO₂) usedas a starting material for the composite. For example, when the silicondioxide (SiO₂) is in the form of spherical particles, the composite mayhave a clumped globular structure, for example, a crumpled paper ballstructure. For example, when the silicon dioxide (SiO₂) is a mesoporoussilicon dioxide, the composite may have a rectangular structure.

In some embodiments, the composite may have a crumpled paper ballstructure in the form of a faceted sphere, and the silicon oxide may bedistributed in the faceted spherical structure. In an embodiment, thecrumpled paper ball structure has an overall shape of a sphere, andcomprises facets on a smaller scale. In an embodiment, the crumpledpaper ball structure comprises graphene microparticles, each of whichhas a planar shape, wherein the combination of graphene microparticleshas an overall spherical shape to provide the crumpled paper ballstructure. The graphene microparticles may have a dimension of 1 nm toabout 500 nm, or about 5 nm to about 100 nm, and the crumpled paper ballstructure may have an overall diameter of about 500 nm to about 5 μm, orabout 600 nm to about 1 μm.

The silicon oxide may be in the form of at least one selected from aparticle, a tube, a wire, a rod, a fiber, and a lump. The silicon oxidemay be bound to the graphene via a chemical bond, for example, acovalent bond or an ionic bond. The covalent bond may include at leastone of, for example, an ester group, an ether group, a carbonyl group,an amide group, and an acid anhydride group.

The ionic bond may be an ionic bond including, for example, carboxylicacid ions, ammonium ions, or acyl cations. The ammonium ions may berepresented by the formula RNH₃ ⁺ (where R may be a hydrogen or at leastone of a C1-C20 alkyl group, a C2-C20 alkenyl group, and a C2-C20alkynyl group).

In some embodiments, the amount of the graphene in the composite may bein a range of about 0.001 parts by weight to about 90 parts by weight,for example, about 10 parts by weight to about 80 parts by weight, basedon 100 parts by weight of the composite. When the amount of the grapheneis within these ranges, the composite may have improved conductivitycharacteristics.

The graphene is a polycyclic aromatic molecule formed of a plurality ofcovalently bonded carbon atoms. The plurality of covalently bondedcarbon atoms may basically form a 6-membered ring as a repeating unit,but may further form a 5-membered ring and/or a 7-membered ring. As aresult, the graphene may appear as a single layer of covalently bondedcarbon atoms (comprising, generally, sp² bonding). The graphene may havea single layer, or a plurality of layers laminated upon one another. Forexample, the graphene may have 1 to about 100 layers, 2 to about 100layers, or about 3 to about 50 layers.

The graphene may extend from the silicon oxide by a distance of about 10nm or less, or about 1 nm to about 10 nm, and may include at least 1 toabout 20 graphene layers, or about 2 to about 18 graphene layers, orabout 3 to about 17 graphene layers, and may have a total thickness ofabout 0.6 nm to about 12 nm, or 0.7 nm to about 11 nm, or 0.8 nm toabout 10 nm. The graphene may be oriented at an angle of about 0° toabout 90°, about 3° to about 85°, or about 5° to about 80° with respectto a primary axis of the silicon oxide.

A proximity of the silicon oxide and the graphene may be evaluated bymeasuring distance between silicon of the silicon oxide and the grapheneby scanning electron microscopy (SEM). The graphene may extend from thesilicon by a distance of 10 nm or less, for example, about 0.5 nm toabout 10 nm, or about 1 nm to about 8 nm. The graphene may be orientedat an angle of about 0° to about 90°, about 3° to about 85°, or about 5°to about 80° with respect to the primary axis of the silicon oxide. Thegraphene may include at least 1 to about 20 graphene layers, or about 2to about 15 graphene layers, and may have a total thickness of about 0.6nm to about 12 nm, about 1 nm to about 11 nm, or about 2 nm to about 10nm. In a preferred embodiment, the graphene may be oriented at an angleof about 0° to 90° with respect to the primary axis of the silicon.

The silicon oxide may have any shape of, for example, but is not limitedto, at least one selected from a nanowire, a particle, a nanotube, ananorod, and a nanoribbon.

In some embodiments, the silicon oxide may be in the form of a nanowire.The nanowire may have a length of less than about 500 nm, for example,about 75 nm to about 400 nm, or about 100 nm to about 300 nm, and adiameter of about 50 nm, for example, about 25 nm to about 125 nm, orabout 50 nm to about 100 nm.

In some embodiments, the composite may be prepared by vapor carbondeposition.

The vapor carbon deposition reaction may include: supplying a carbonsource gas to contact the carbon source gas with silicon dioxide (SiO₂),wherein the carbon source gas may be i) a compound represented byFormula 2 or ii) a mixed gas of a compound represented by Formula 2 andat least one selected from a compound represented by Formula 1 and anoxygen-containing gas represented by Formula 3; and thermally treatingthe contacted silicon oxide.

C_(n)H_((2n+2−a))[OH]_(a)  Formula 1

wherein, in Formula 1, may be an integer of 1 to 20, and a may be 0 or1,

C_(n)H_((2n))  Formula 2

wherein, in Formula 2, n may be an integer of 2 to 6, and

CxHyOz  Formula 3

wherein, in Formula 3, x may be 0 or an integer of 1 to 20, y may be 0or an integer of 1 to 20, and z may be 1 or 2.

Although not wanting to be limited to any specific theory, such coatingby the above-described vapor carbon deposition is understood to beassociated with reforming of the silicon dioxide (SiO₂) in the mixed gaswith CO₂. For example, when the compound of Formula 1 is methane (i.e.,where n in Formula 1 is 1 and a is 0), it may be supposed thatdeposition of carbon on silicon oxide may occur from a side reaction(e.g., a Boudouard reaction represented by Reaction Scheme 2) or areformation reaction represented by Reaction Scheme 1, or from thedecomposition reaction of the compound of Formula 1 as represented byReaction Scheme 3.

However, other reactions, not limited to the above-described reactions,may occur during the thermal treatment in the vapor carbon depositionreaction.

According to the above-described vapor carbon deposition, graphene maybe directly grown on the silicon of silicon oxide product (SiO_(x)), andthus may have a high proximity to the silicon.

In some embodiments, graphene may be grown on the silicon oxide byreaction of a carbon-containing gas and an oxygen-containing gas to formthe composite.

FIG. 1 is a schematic view of an embodiment of a method of preparing acomposite. However, embodiments of the present disclosure are notlimited to the scheme shown in FIG. 1, which is merely presented as anexample.

Referring to FIG. 1, a reaction gas including a carbon source gas issupplied to contact a silicon dioxide (SiO₂) particle 10 to provideSiO_(x) where 0<x≤2 having graphene 11 thereon, and thus graphene 11 maydisposed, e.g., grown, on at least one silicon oxide particle 10a(SiO_(x) where 0<x≤2). The graphene 11 may also be gradually grown onat least one second silicon oxide particle 10 b (SiO_(x) where 0<x≤2),resulting from the lapse of reaction time to thus obtain a composite.

For example, the composite may have a structure in which at least onethird silicon oxide particle 10 c is distributed in the graphene 11.

In FIG. 1, the silicon dioxide (SiO₂) particle 10, the at least onefirst silicon oxide particle 10 a (SiO_(x)), the at least one secondsilicon oxide particle 10 b, and the at least one third silicon oxideparticle 10 c, resulting from the lapse of reaction time, may appear tohave different sizes, but are not limited thereto. The silicon oxideparticles 10, 10 a, 10 b, and 10 c, may each independently have adiameter of 10 nm to 500 nm, or about 20 nm to about 400 nm. Althoughnot illustrated in detail, the graphene 11 in FIG. 1 may have astructure of layer or nanosheet, or a structure including flakes.

As used herein, the terms “nanosheet” and “layer” may be defined asfollows.

The term “nanosheet” may refer to graphene formed in an irregularpattern on the silicon oxide (SiO_(x)), and the term “layer” may referto graphene formed as a continuous uniform pattern on the silicon oxide(SiO_(x)). The term “flake” may refer to the case where the nanosheet orlayer is partially damaged or deformed.

In some embodiments, the amount of the graphene in the composite may bein a range of about 0.001 parts by weight to about 90 parts by weight,for example, about 10 parts by weight or about 80 parts by weight, basedon 100 parts by weight of the composite. When the amount of the grapheneis within these ranges, the composite may have improved conductivity.

According to another aspect of the present disclosure, anelectrochemically active material composite includes the compositeaccording to the above-described embodiments and an electrochemicallyactive material.

Charging and discharging may be performed at a high voltage to increasethe capacity of a battery. While not wanting to be bound by theory, itis understood that during such charging and discharging, decompositionof the electrolyte, or dissolution and electrochemical deposition of anactive metallic material may occur on a surface of the cathode of thebattery. Such side reactions on the surface of the cathode mayconsequently lead to self-discharging of the battery during storage athigh temperature and reduction in capacity during high-temperaturecharging and discharging.

While not wanting to be bound by theory, it is understood that using thecomposite disclosed herein or an electrochemically active materialcomposite comprising the composite may reduce a side reaction resultingfrom the direct contact of the electrolyte to the electrode surface andelectron transfer therebetween, and may also remove a byproduct that mayresult from charging and discharging and deteriorate cell performance.

Hereinafter, an embodiment of a method of preparing the composite, willbe disclosed in greater detail.

A method of preparing a composite, according to an embodiment of thepresent disclosure, may include contacting a reaction gas including acarbon source gas and silicon dioxide (SiO₂); and thermally treating thereaction gas-contacted silicon dioxide to prepare the composite.

The carbon source gas may be i) a compound represented by Formula 2, orii) a mixed gas of a compound represented by Formula 2 and at least oneselected from a compound represented by Formula 1 and anoxygen-containing gas represented by Formula 3.

C_(n)H_((2n+2−a))[OH]_(a)  Formula 1

wherein, in Formula 1, n may be an integer of 1 to 20, and a may be 0 or1,

C_(n)H_((2n))  Formula 2

wherein, in Formula 2, n may be an integer of 2 to 6,

C_(x)H_(y)O_(z)  Formula 3

wherein, in Formula 3, x may be 0 or an integer of 1 to 20, y may be 0or an integer of 1 to 20, and z may be 1 or 2.

The compound represented by Formula 1 or the compound represented byFormula 2 may be at least one selected from methane, ethylene,propylene, methanol, ethanol, and propanol.

The oxygen-containing gas represented by Formula 3 may include, forexample, at least one selected from carbon dioxide (CO₂), carbonmonoxide (CO), and water vapor (H₂O).

The method of preparing a composite may further include cooling with atleast one inert gas selected from nitrogen, helium, and argon after thethermally treating of the reaction gas-contacted silicon dioxide (SiO₂).The cooling refers to controlling the temperature to room temperature(about 20° C. to about 25° C.).

The carbon source gas may include at least one inert gas selected fromnitrogen, helium, and argon.

The oxygen-containing gas may be at least one selected from carbonmonoxide, carbon dioxide, and water vapor.

In some embodiments, the graphene in the composite may have, forexample, a layered structure including about 1 to about 20 layers, orabout 5 to about 10 layers.

FIG. 2 is a graph for explaining growing of graphene by a vapordeposition reaction and discloses reaction conditions such astemperature, time, and reaction gas composition in an embodiment of amethod of preparing a composite.

Referring to FIG. 2, processes 1 and 2 illustrate an embodiment of amethod of preparing a composite. Process 1 may include supplying methane(CH₄) and increasing a temperature to a thermal treatment temperature(T). A temperature increase time (h1) may be about 10 minutes to about 4hours, about 20 minutes to about 3.5 hours, or about 30 minutes to about3 hours, and the thermal treatment temperature (T) may be in a range ofabout 700° C. to about 1100° C., about 750° C. to about 1050° C., orabout 800° C. to about 1000° C.

In process 1, thermal treatment may be performed at the thermaltreatment time (T) for a reaction time (h4−h1), and then a product fromthe thermal treatment may be cooled down to room temperature to obtain acomposite product. The time it takes to cool down to room temperature(h5−h4) may be, for example, about 1 to about 5 hours, about 1.5 toabout 4.5 hours, or about 2 to about 4 hours.

The reaction time (h4−h1) may be, for example, about 4 to about 8 hours,about 4.5 to about 7.5 hours, or about 5 to about 7 hours.

Process 2 is the same as process 1, except that an initial reaction gashaving a different composition is used, and nitrogen is supplied duringthe cooling to room temperature after the thermal treatment. Thecomposite prepared by process 2 may include an increased amount ofgraphene and have a larger specific surface area and a largerconductivity, compared to the composite prepared by process 1.

Process 3 illustrates preparing a composite by a vapor depositionmethod. Process 3 may involve supplying hydrogen, increasing atemperature to a thermal treatment temperature T, a thermal treatment atthe thermal treatment temperature T, supplying a mixed gas of methaneand hydrogen at the thermal treatment temperature T, and cooling whilesupplying nitrogen.

In the methods of preparing a composite, according to theabove-described embodiments of the present disclosure, when the carbonsource gas includes water vapor, a composite having improvedconductivity may be obtained. Although not limited to any specifictheory, the high conductivity of the composite even with coating of lessamount of carbon is attributed to the deposition of carbon having highcrystallinity on the silicon oxide of the formula SiO_(x) wherein 0<x≤2by reaction of the gas mixture in the presence of water vapor. Theamount of water vapor in the gas mixture, although not specificallylimited, may be, for example, in a range of about 0.01% by volume (vol%) to about 10 vol %, 0.05% by volume (vol %) to about 8 vol %, or 0.1%by volume (vol %) to about 5 vol %, based on a total volume of thecarbon source gas.

In some embodiments, the carbon source gas may be methane, a mixed gasof methane and an inert gas, an oxygen-containing gas, or a mixed gas ofmethane and an oxygen-containing gas.

In some embodiments, the carbon source gas may be i) CH₄, ii) a mixedgas of CH₄ and CO₂, or iii) a mixed gas of CH₄, CO₂, and H₂O.

The mixed gas of CH₄ and CO₂ may be supplied to have a mole ratio of CH₄and CO₂ of about 1:0.2 to about 1:0.5, and in some embodiments, in amole ratio of about 1:0.25 to about 1:0.45, and in some otherembodiments, in a mole ratio of about 1:0.3 to about 1:0.4.

In the mixed gas of CH₄, CO₂, and H₂O, the amount of CO₂ is in the rangeof about 0.20 mole to about 0.50 mole, and in some embodiments, in therange of about 0.25 mole to about 0.45 mole, and in some otherembodiments, in the range of about 0.30 mole to about 0.40 mole, basedon 1 mole of CH₄. Also, the amount of H₂O is in the range of about 0.01mole to about 1.45 mole, and in some embodiments, in the range of about0.10 mole to about 1.35 mole, and in some other embodiments, in therange of about 0.05 mole to about 1.0 mole, based on 1 mole of CH₄.

In some embodiments, the carbon source gas may be carbon monoxide (CO)or carbon dioxide (CO₂).

In some embodiments, the carbon source gas may be a mixed gas of CH₄ andN2.

The mixed gas of CH₄ and N2 may be supplied in a mole ratio of CH₄ andN2 of about 1:0.2 to about 1:0.5, and in some embodiments, in a moleratio of about 1:0.25 to 1:0.45, and in some other embodiments, in amole ratio of about 1:0.3 to about 1:0.4. In some embodiments, thecarbon source gas may not include an inert gas such as nitrogen.

The thermal treatment may be performed at a temperature of about 700° C.to about 1100° C., about 750° C. to about 1050° C., or about 800° C. toabout 1000° C.

The thermal treatment may be performed without limitation to a selectedpressure. The pressure level for the thermal treatment may beappropriately selected in consideration of the thermal treatmenttemperature, composition of the gas mixture, and target amount of coatedcarbon. The pressure level for the thermal treatment may be controlledby varying the amounts of inflow and outflow of the gas mixture. Forexample, the pressure for the thermal treatment may be about 1atmosphere (atm) or greater, and in some embodiments, about 2 atm orgreater, about 3 atm or greater, about 4 atm or greater, or about 5 atmor greater, but is not limited thereto. In an embodiment the pressurefor the thermal treatment may be about 1 atmosphere to about 50 atm,about 2 atm to about 45 atm, or about 4 atm to about 40 atm.

The thermal treatment time may be not specifically limited, and may beappropriately controlled depending on the thermal treatment temperature,thermal treatment pressure, composition of the gas mixture, and targetamount of coated carbon. For example, the thermal treatment time may bein a range of about 10 minutes to about 100 hours, and in someembodiments, may be in a range of about 30 minutes to about 90 hours,and in some other embodiments, may be in a range of about 50 minutes toabout 40 hours, but is not limited thereto. Although not limited to anyspecific theory, the longer the thermal treatment time, the more theamount of graphene (carbon) may be deposited, and the better theelectrical characteristics of the composite may become. However, theseeffects may not be directly proportional to the thermal treatment time.For example, deposition of graphene may not occur any longer after apredetermined duration, or the deposition rate may become low.

The disclosed methods of preparing the composite, according to theabove-described embodiments of the present disclosure, may providegraphene which is uniformly coated on the silicon oxide (SiO_(x)), evenat a relatively low temperature by vapor deposition of the carbon sourcegas as described above.

The coating of graphene on the silicon oxide (SiO_(x)) by vapordeposition may form a coating layer having high crystallinity on thecomposite. When the composite having such a highly-crystalline coatinglayer is used as an anode active material, the anode active material mayhave improved conductivity without structural change.

An electrochemically active material composite using the compositeaccording to the above-described embodiments may be prepared as follows.

The disclosed composite may be mixed with an electrochemically activematerial to obtain a mixture of the composite and the electrochemicallyactive material.

The mixing may be performed using a Nobita mixer. The mixing may beperformed at a mixing rate of about 100 revolutions per minute (rpm) toabout 800 rpm, for example, at about 300 rpm. The mixing time may varydepending on the mixing rate. For example, the mixing time may be in arange of about 10 minutes to about 100 minutes.

The amount of the composite in the mixture of the composite and theelectrochemically active material may be in a range of about 0.1 partsby weight to about 100 parts by weight, for example, about 0.5 parts byweight to about 30 parts by weight, based on 100 parts by weight of themixture.

Any of the composite or the electrochemically active material compositeaccording to the above-described embodiment may be used in an electrodeand a battery. For example, a composite according to any of theabove-described embodiment may be used, for example, as an electrodeactive material, or a conducting agent for enhancing the bindingstrength between an electrode and an active material.

In some embodiments, the composite may be used as a field emissionmaterial for a display, or may be used in a thermoelectric device or abiosensor.

According to another aspect of the present disclosure, an electrodeincludes the composite or the electrochemically active materialcomposite according to any of the above-described embodiments. Theelectrode may be an electrode for a lithium battery.

The electrode may be a cathode or an anode.

According to another aspect of the present disclosure, a lithium batteryincludes a composite or an electrochemically active material compositeaccording to any of the above-described embodiments, theelectrochemically active material composite including the composite andan electrochemically active material.

The electrochemically active material may be a commercially availablecathode active material or a commercially available anode activematerial.

The cathode active material may include at least one selected fromlithium cobalt oxide, lithium nickel cobalt manganese oxide, lithiumnickel cobalt aluminum oxide, lithium iron phosphorous oxide, andlithium manganese oxide, but is not limited thereto. Any suitablecathode active material available in the art may be used.

For example, the cathode active material may be a compound representedby one of the following formulas: Li_(a)A_(1-b)B′_(b)D′₂ (where0.90≤a≤1.8, and 0≤b≤0.5); Li_(a)E_(1-b)B′_(b)O_(2-c)D′_(c) (where0.90≤a≤1.8, 0≤b≤0.5, and 0≤c≤0.05); LiE_(2-b)B′_(b)O_(4-c)D′_(c) (where0≤b≤0.5, and 0≤c≤0.05); Li_(a)Ni_(1-b-c)CO_(b)B′_(c)D′_(α) (where0.90≤a≤1.8, 0≤b≤0.5, 0≤c≤0.05, and 0<α≤2);Li_(a)Ni_(1-b-c)CO_(b)B′_(c)O_(2-α)F′_(α) (where 0.90≤a≤1.8, 0≤b 0.5,0≤c≤0.05, and 0<α<2); Li_(a)Ni_(1-b-c)CO_(b)B′_(c)O_(2-α)F′₂ (where0.90≤a≤1.8, 0≤b 0.5, 0≤c≤0.05, and 0<α<2);Li_(a)Ni_(1-b-c)Mn_(b)B′_(c)D′_(α) (where 0.90≤a≤1.8, 0≤b≤0.5, 0≤c≤0.05,and 0<α≤2); Li_(a)Ni_(1-b-c)Mn_(b)B′_(c)O_(2-α)F′_(α) (where 0.90≤a≤1.8,0≤b≤0.5, 0≤c≤0.05, and 0<α<2); Li_(a)Ni_(1-b-c)Mn_(b)B′_(c)O_(2-α)F′₂(where 0.90≤a≤1.8, 0≤b≤0.5, 0≤c≤0.05, and 0<a<2);Li_(a)Ni_(b)E_(c)G_(d)O₂ (where 0.90≤a≤1.8, 0≤b≤0.9, 0≤c≤0.5, and0.001≤d≤0.1); Li_(a)Ni_(b)Co_(c)Mn_(d)GeO₂ (where 0.90≤a≤1.8, 0≤b≤0.9,0≤c≤0.5, 0≤d≤0.5, and 0.001≤e≤0.1); Li_(a)NiG_(b)O₂ (where 0.90≤a≤1.8,and 0.001≤b≤0.1); Li_(a)CoG_(b)O₂ (where 0.90≤a≤1.8, and 0.001≤b≤0.1);Li_(a)MnG_(b)O₂ (where 0.90≤a≤1.8, and 0.001≤b≤0.1); Li_(a)Mn₂G_(b)O₄(where 0.90≤a≤1.8, and 0.001≤b≤0.1); QO₂; QS₂; LiQS₂; V₂O₅; LiV₂O₅;LiI′O₂; LiNiVO₄; Li_((3-f))J₂(PO₄)₃ (where 0≤f≤2); Li_((3-f))Fe₂(PO₄)₃(where 0≤f≤2); and LiFePO₄.

In the formulas above, A is at least one selected from nickel (Ni),cobalt (Co), and manganese (Mn); B′ is at least one selected fromaluminum (Al), nickel (Ni), cobalt (Co), manganese (Mn), chromium (Cr),iron (Fe), magnesium (Mg), strontium (Sr), vanadium (V), and a rareearth element; D′ is at least one selected from oxygen (O), fluorine(F), sulfur (S), and phosphorus (P); E is at least one selected fromcobalt (Co), and manganese (Mn); F′ is at least one selected fromfluorine (F), sulfur (S), and phosphorus (P); G is at least one selectedfrom aluminum (Al), chromium (Cr), manganese (Mn), iron (Fe), magnesium(Mg), lanthanum (La), cerium (Ce), strontium (Sr), and vanadium (V); Qis at least one selected from titanium (Ti), molybdenum (Mo), andmanganese (Mn); I′ is at least one selected from chromium (Cr), vanadium(V), iron (Fe), scandium (Sc), and yttrium (Y); and J is at least oneselected from vanadium (V), chromium (Cr), manganese (Mn), cobalt (Co),nickel (Ni), and copper (Cu).

The cathode active material may be, for example, a compound representedby Formula 4, a compound represented by Formula 5, or a compoundrepresented by Formula 6.

Li_(a)Ni_(b)Co_(c)Mn_(d)O₂  Formula 4

In Formula 4, 0.90≤a≤1.8, 0≤b≤0.9, 0≤c≤0.5, 0≤d≤0.5.

Li₂MnO₃  Formula 5

LiMO₂  Formula 6

In Formula 6, M may be at least one selected from Mn, Fe, Co, and Ni.

The cathode active material may be, for example,LiNi_(0.5)Co_(0.2)Mn_(0.3)O₂. In some embodiments, the cathode activematerial may be a compound represented by Formula 7.

yLi[Li_(1/3)Me_(2/3)]O₂-(1−y)LiMe′O₂  Formula 7

In Formula 7, 0<y<1; Me may be at least one selected from Mn, Mo, W, V,Ti, Zr, Ru, Rh, Pd, Os, Ir, and Pt; and Me′ may be at least one selectedfrom Ni, Co, Mn, Cr, Zr, Nb, Cu, V, Ti, Zn, Al, Ga, Mg, and boron (B).For example, Me′ may be at least one selected from Ni, Mn, and Co.

In Formula 7, for example, 0<y<≤0.8.

In Formula 7, Me may be represented by Formula 8.

M′_(a)M_(b)Mn_(c)  Formula 8

In some embodiments, in Formula 8,

M may be at least one selected from molybdenum (Mo), tungsten (W),vanadium (V), titanium (Ti), zirconium (Zr), ruthenium (Ru), rhodium(Rh), palladium (Pd), osmium (Os), iridium (Ir), and platinum (Pt),

M′ may be at least one selected from nickel (Ni), copper (Cu), zinc(Zn), cobalt (Co), chromium (Cr), iron (Fe), and magnesium (Mg),

0≤a≤0.33, 0≤b≤0.33, and a+b+c=1.

The cathode active material may be at least one selected from compoundsrepresented Formulas 9 to 12.

Li_(x)Co_(1-y-z)Ni_(y)M_(z)O_(2-a)X_(a)  Formula 9

In Formula 9, 0.9≤x≤1.6, 0≤y≤1, 0≤z≤1, 0≤a≤1, X may be at least oneselected from oxygen (O), fluorine (F), sulfur (S), and phosphorous (P),and M may be at least one selected from Ni, Co, Mn, Cr, Zr, Nb, Cu, V,Ti, Zn, Al, Ga, Mg, and boron (B).

Li_(x)Mn_(2-y)M_(y)O_(4-a)X_(a)  Formula 10

In Formula 10, 0.9≤x≤1.6, 0≤y≤1, 0≤z≤0.5, 0≤a≤1, X may be at least oneselected from oxygen (O), fluorine (F), sulfur (S), and phosphorous (P),and M may be at least one selected from Ni, Co, Mn, Cr, Zr, Nb, Cu, V,Ti, Zn, Al, Ga, Mg, and boron (B).

MFePO₄  Formula 11

In Formula 11, M may be at least one selected from Ni, Co, Mn, Cr, Zr,Nb, Cu, V, Ti, Zn, Al, Ga, Mg, and B,

Li_(x)M_(y)M′_(z)PO_(4-d)X_(d)  Formula 12

In Formula 12, 0.9≤x≤1.1, 0≤y≤l, 0≤z≤1, 1.9≤x+y+z≤2.1, 0≤d≤0.2, M may beat least one selected from the group consisting of Fe, Mn, Ni, and Co,M′ may be at least one selected from Mg, Ca, Sr, Ba, Ti, Zr, Nb, Mo, W,Zn, Al, Si, Cr, Zr, Nb, Cu, V, Ti, Zn, Ga, and B, and X may be at leastone selected from the group consisting of S and F.

In Formulas 9 and 10, x may be in a range of about 1.1 to about 1.6.

In some embodiments, the cathode active material may be selected fromLi_(1.18)Ni_(0.17)Co_(0.1)Mn_(0.56)O₂, LiCoO₂, LiFePO₄,LiFe_(1-a)Mn_(a)PO₄ (0<a<1), LiNi_(0.5)Mn_(1.5)O₄, and LiMnPO₄.

An anode active material may be used as the electrochemically activematerial. For example, the anode active material may be a structure witha metal nanowire disposed on a carbonaceous base. The amount of thecarbonaceous base may be in a range of about 1 part by weight to about20 parts by weight, based on 100 parts by weight of the structure.

The metal nanowire may be, for example, a silicon oxide nanowire.

The carbonaceous base may comprise graphite. For example, the graphitemay be SFG6 graphite (TimCal Co.), and may have an average particlediameter of about 16 micrometers (μm). The metal nanowire may have adiameter of about 50 nm and a length of about 400 nm.

In an electrode formed using an electrochemically active materialcomposite according to any of the above-described embodiments, theamount of the electrochemically active material composite may be, forexample, in a range of about 68 parts by weight to about 87 parts byweight, based on 100 parts by weight of the electrode. The amount of thebinder may be in a range of about 13 parts by weight to about 32 partsby weight, based on 100 parts by weight of the electrode. An example ofthe binder is lithium polyacrylate (LiPAA).

A battery having improved capacity and good improved ratecharacteristics may be manufactured using an electrochemically activematerial composite according to any of the above-described embodiments.

An electrochemically active material composite according to any of theabove-described embodiments may be used as an electrode active materialas described above, and may also be used alone without a commonconducting agent when prepared as a composite with a conducting agent.

The electrochemically active material composite may reduce the specificsurface area of the electrochemically active material, and thus mayimprove the binding strength between a current collector and theelectrochemically active material and the binding strength between theelectrochemically active materials when used to form an electrode.

A cathode may be manufactured as follows.

First, a cathode active material, a binder, and a solvent are mixed toprepare a cathode active material composition. A conducting agent may befurther added into the cathode active material composition.

The cathode active material composition may be directly coated on ametallic current collector and dried to form a cathode plate.Alternatively, the cathode active material composition may be cast on aseparate support to form a cathode active material film, which may thenbe separated from the support and laminated on a metallic currentcollector to form a cathode plate.

An electrochemically active material composite according to any of theabove-described embodiment may be used as the cathode active material.

The cathode may further include an additional cathode active material asused in a lithium battery, in addition to the electrochemically activematerial composite.

The additional cathode active material may be at least one selected fromlithium cobalt oxide, lithium nickel cobalt manganese oxide, lithiumnickel cobalt aluminum oxide, lithium iron phosphorous oxide, andlithium manganese oxide, but is not limited thereto. Any suitablecathode active material available in the art may be used.

The compounds listed above as an additional cathode active material mayhave a surface coating layer (hereinafter, a “coating layer”).Alternatively, a mixture of a compound without having a coating layerand a compound having a coating layer, the compounds being selected fromthe compounds listed above, may be used. The coating layer may includeat least one compound of a coating element selected from an oxide,hydroxide, oxyhydroxide, oxycarbonate, and hydroxycarbonate of thecoating element. The compounds for the coating layer may be amorphous orcrystalline. The coating element for the coating layer may be at leastone selected from magnesium (Mg), aluminum (Al), cobalt (Co), potassium(K), sodium (Na), calcium (Ca), silicon (Si), titanium (Ti), vanadium(V), tin (Sn), germanium (Ge), gallium (Ga), boron (B), arsenic (As),and zirconium (Zr). The coating layer may be formed using any suitablemethod that does not adversely affect the physical properties of thecathode active material when a compound of the coating element is used.For example, the coating layer may be formed using a spray coatingmethod, a dipping method, or the like. The details of the coating methodcan be determined by one of skill in the art without undueexperimentation, and thus a detailed description thereof will beomitted.

The conducting agent, binder, and solvent used in the cathode activematerial composition may be the same as those used in an anode activematerial composition described above. If desired, a plasticizer may befurther added to the cathode active material composition and/or theanode active material composition to form pores in the electrode plates.

The amounts of the cathode active material, the conducting agent, thebinder, and the solvent may be those levels that are generally used inthe manufacture of lithium batteries in the art. At least one of theconducting agent, the binder and the solvent may be omitted depending onthe use and the structure of a lithium battery.

An anode may be manufactured in a substantially same manner as in themanufacture of the cathode, except for using an anode active materialinstead of a cathode active material.

Examples of the anode active material are at least one selected from acarbonaceous material, silicon, a silicon oxide, a silicon-based alloy,a silicon-carbonaceous material composite, tin, a tin-based alloy, atin-carbon composite, and a metal oxide.

Examples of the carbonaceous material are crystalline carbon, amorphouscarbon, and mixtures thereof. Non-limiting examples of the crystallinecarbon are graphite, such as natural graphite or artificial graphitethat are in amorphous, plate, flake, spherical or fibrous form.Non-limiting examples of the amorphous carbon are soft carbon (carbonsintered at low temperatures), hard carbon, meso-phase pitch carbides,sintered corks, graphene, carbon black, fullerene soot, carbonnanotubes, and carbon fibers. Any appropriate material available in theart may be used.

For example, the anode active material may be selected from Si, SiO_(x)(where 0<x<2, for example, 0.5≤x≤1.5), Sn, SnO₂, a silicon-containingmetal alloy, and mixtures. A metal alloyable with silicon may be atleast one selected from Al, Sn, Ag, Fe, Bi, Mg, Zn, in, Ge, Pb, and Ti.

The anode active material may include a metal/metalloid alloyable withlithium, an alloy thereof, or an oxide thereof. Examples of themetal/semimetalloid alloyable with lithium are Si, Sn, Al, Ge, Pb, Bi,Sb, a Si—Y′ alloy (where Y′ is an alkali metal, an alkaline earth metal,a Group 13 element, a Group 14 element, a transition metal, a rare earthelement, or a combination thereof except for Si), a Sn-Y″ alloy (whereY″ is an alkali metal, an alkaline earth metal, a Group 13 element, aGroup 14 element, a transition metal, a rare earth element, or acombination thereof except for Sn), and MnO_(x) (where 0<×52). Y may bemagnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), radium (Ra),scandium (Sc), yttrium (Y), titanium (Ti), zirconium (Zr), hafnium (Hf),rutherfordium (Rf), vanadium (V), niobium (Nb), tantalum (Ta), dubnium(Db), chromium (Cr), molybdenum (Mo), tungsten (W), seaborgium (Sg),technetium (Tc), rhenium (Re), bohrium (Bh), iron (Fe), lead (Pb),ruthenium (Ru), osmium (Os), hassium (Hs), rhodium (Rh), iridium (Ir),palladium (Pd), platinum (Pt), copper (Cu), silver (Ag), gold (Au), zinc(Zn), cadmium (Cd), boron (B), aluminum (Al), gallium (Ga), tin (Sn),indium (In), titanium (Ti), germanium (Ge), phosphorus (P), arsenic(As), antimony (Sb), bismuth (Bi), sulfur (S), selenium (Se), tellurium(Te), polonium (Po), or combinations thereof. Non-limiting examples ofthe oxide of the metal/metalloid alloyable with lithium are a lithiumtitanium oxide, a vanadium oxide, and a lithium vanadium oxide, SnO₂,and SiO_(x) (where 0<x<2).

For example, the anode active material may include at least one elementselected from the elements of Groups 13, 14, and 15 of the periodictable of elements.

In some other embodiments, the anode active material may include atleast one element selected from Si, Ge, and Sn.

The amounts of the anode active material, conducting agent, binder, andsolvent may be those levels that are generally used in the manufactureof lithium batteries in the art.

A separator may be disposed between the cathode and the anode. Theseparator may be an insulating thin film having high ion permeabilityand strong mechanical strength.

The separator may have a pore diameter of about 0.01 μm to about 10 μmand a thickness of about 5 μm to about 20 μm. Examples of the separatorare olefin-based polymers, such as polypropylene, and sheets ornon-woven fabric made of glass fiber or polyethylene. When a solidpolymer electrolyte is used, the solid polymer electrolyte may alsoserve as the separator.

The separator may be a monolayer or a multilayer including at least twolayers of olefin-based polymer, for example, polyethylene,polypropylene, polyvinylidene fluoride, or a combination thereof. Forexample, the separator may be a two-layered separator includingpolyethylene and polypropylene layers, a three-layered separatorincluding polyethylene, polypropylene and polyethylene layers, or athree-layered separator including polypropylene, polyethylene andpolypropylene layers.

In the preparation of lithium battery, a lithium salt-containingnon-aqueous electrolyte is used. The lithium salt-containing non-aqueouselectrolyte may include a non-aqueous electrolyte and a lithium salt.

The non-aqueous electrolyte may be a non-aqueous liquid electrolyte, anorganic solid electrolyte, or an inorganic solid electrolyte.

The non-aqueous liquid electrolyte may include an organic solvent. Theorganic solvent may be any organic solvent available in the art.Examples of the organic solvent are propylene carbonate, ethylenecarbonate, fluoroethylene carbonate, butylene carbonate, dimethylcarbonate, diethyl carbonate, methylethyl carbonate, methylpropylcarbonate, ethylpropyl carbonate, methylisopropyl carbonate, dipropylcarbonate, dibutyl carbonate, chloroethylene carbonate, benzonitrile,acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran, γ-butyrolactone,dioxorane, 4-methyldioxorane, N,N-dimethyl formamide, N,N-dimethylacetamide, N,N-dimethylsulfoxide, dioxane, 1,2-dimethoxyethane,sulforane, dichloroethane, chlorobenzene, nitrobenzene, diethyleneglycol, dimethyl ether, or mixtures thereof.

Examples of the organic solid electrolyte are polyethylene derivatives,polyethylene oxide derivatives, polypropylene oxide derivatives,phosphoric acid ester polymers, poly agitation lysine, polyestersulfide, polyvinyl alcohols, polyvinylidene fluoride, and polymerscontaining ionic dissociation groups.

Non-limiting examples of the inorganic solid electrolyte are nitrides,halides, and sulfates of lithium, such as Li₃N, LiI, Li₅NI₂,Li₃N—LiI-LiOH, Li₂SiS₃, Li₄SiO₄, Li₄SiO₄-LiI—LiOH, and Li₃PO₄—Li₂S—SiS₂.

The lithium salt may be a material dissoluble in the non-aqueouselectrolyte, for example, LiPF₆, LiBF₄, LiSbF₆, LiAsF₆, LiClO₄,LiCF₃SO₃, Li(CF₃SO₂)₂N, LiC₄F₉SO₃, LiAlO₂, LiAlCl₄,LiN(C_(x)F_(2x+1)SO₂)(C_(y)F_(2y+1)SO₂) (where x and y are naturalnumbers), LiCl, LiI, or a mixture thereof. An additive to improve chargeand discharge characteristics and resistance to flame may be added tothe non-aqueous electrolyte. Examples of the additive are pyridine,triethylphosphite, triethanolamine, cyclic ethers, ethylenediamine,n-glyme, hexamethylphosphoramide, nitrobenzene derivatives, sulfur,quinine imine dyes, N-substituted oxazolidinone, N, N-substitutedimidazolidine, ethylene glycol dialkyl ether, ammonium salts, pyrrole,2-methoxyethanol, and aluminum trichloride. A halogen-containingsolvent, such as carbon tetrachloride, ethylene trifluoride, or thelike, may be further added to provide non-flammability.

FIG. 3A is a schematic view of a lithium battery 131 according to anembodiment of the present disclosure. Referring to FIG. 3A, the lithiumbattery 131 includes a cathode 133, an anode 132, and a separator 34.The cathode 133, the anode 132 and the separator 134 may be wound orfolded, and then sealed in a battery case 135. Then, the battery case135 is filled with an organic electrolyte solution and sealed with a capassembly 136, thereby completing the manufacture of the lithium battery131. The battery case 135 may be a cylindrical type, a rectangular type,or a thin-film type. For example, the lithium battery 131 may be athin-film type battery. For example, the lithium battery 131 may be alithium ion battery.

The separator 134 may be interposed between the cathode 133 and theanode 32 to form a battery assembly. A plurality of such batteryassemblies may be stacked in a bi-cell structure and impregnated with anorganic liquid electrolyte. The resultant is then put into a pouch andhermetically sealed to manufacture a lithium ion battery.

Alternatively, a plurality of battery assemblies may be stacked upon oneanother to form a battery pack, which may be used in any device thatoperates at high temperatures and requires high output, for example, ina laptop computer, a smart phone, electric vehicle, and the like.

A lithium battery including such a battery pack may have improved highrate characteristics and lifetime characteristics, and thus may beapplicable in an electric vehicle (EV), for example, in a hybrid vehiclesuch as plug-in hybrid electric vehicle (PHEV).

The lithium battery including such a battery pack may have improvedconductivity, and consequently exhibit a higher initial charge-dischargeefficiency and a higher capacity. Due to reduced resistance against therate of charging and discharging, the lithium battery may be charged ordischarged at high rates. In particular, a side reaction on the surfaceof a cathode and decomposition of the electrolyte on the surface of thecathode may be effectively prevented, so that the lithium battery mayhave a longer lifetime and improved durability.

According to another aspect of the present disclosure, a field emissiondevice includes the composite.

A field emission device is a device using migration of electrons. Ingeneral, a field emission device may include, at least, a reductionelectrode, an emitter tip, and an oxidation electrode separated from thereduction electrode (see U.S. Pat. Nos. 7,009,331, 6,976,897, and6,911,767, and US 2006/0066217, the contents of which are incorporatedherein in their entirety by reference). The emitter tip may emitelectrons as a voltage is applied between the reduction electrode andthe oxidation electrode. The electrons may migrate from the reductionelectrode toward the oxidation electrode. An field emission deviceaccording to an embodiment of the present disclosure may be used forvarious purposes, for example, in an ultrasonic vacuum tube equipment(for example, X-ray tube), a power amplifier, an ion gun, a high-energyaccelerator, a free-electron laser, and an electron microscope, andspecifically, in a flat display device. A flat display device may beused as an alternative to a cathode tube, and thus may also beapplicable in a TV or a computer monitor.

A composite according to any of the above-described embodiments may beused as the emitter tip.

An emitter tip may be manufactured using a metal such as molybdenum (Mo)or a semiconductor such as silicon. One of the concerns with using themetal emitter is the comparatively high control voltage of about 100 Vrequired for emission. In addition, due to nonuniformity of such emittertips, current densities of individual pixels of a field emission deviceusing the metal emitter tips may be nonuniform.

However, when an emitter tip using a composite according to any of theabove-described embodiments is used, the field emission device may haveimproved field emission characteristics.

The composite according to any of the above-described embodiments may beused to prepare an electroluminescent device.

According to another aspect of the present disclosure, a biosensorincludes the composite.

The composite according to any of the above-described embodiments may beused to form an electrode of the biosensor.

FIG. 3E is a schematic cross-sectional view illustrating a structure ofan electrode of a biosensor according to an embodiment of the presentdisclosure.

Referring to FIG. 3E, the electrode of the biosensor includes asubstrate 310, a first layer 320 disposed on the substrate 310 andincluding a composite, and a second layer 330 disposed on the firstlayer 320. A biomaterial 340 may be supported or fixed in the secondlayer 330 in a variety of manners.

The substrate 310 may be any plate on which graphene may be deposited orformed, and for example, may be selected from the group consisting ofglass, plastic, metal, ceramic, and silicon. A type of the substrate 310is not specifically limited, provided that graphene may be deposited orformed thereon.

The biomaterial 340 may be selected from enzymes, aptamers, proteins,nucleic acids, microorganisms, cells, lipids, hormones, DNA, PNA, RNA,and a mixture thereof. Any suitable biomaterial may also be used.

Referring to FIG. 3E, in the electrode of a biosensor, the biomaterial340 may be an enzyme, and the first layer 320 may be a layer able tosupport or fix the enzyme therein.

Although in FIG. 3E an enzyme as the biomaterial 340 appears to besupported or fixed in the first layer 320, the location of the enzyme isnot limited thereto, and a part or the whole enzyme may protrude throughthe surface of the first layer 320 and be exposed. When a biosensor hasthis structure including an enzyme with substrate specificity toselectively respond to a target molecule in a mixture, the biosensor mayselectively sense an analyte (for example, blood sugar) that responds tothe enzyme.

According to another aspect of the present disclosure, a semiconductordevice includes the composite.

The composite may be used as an electrode of the semiconductor device.

According to another aspect of the present disclosure, there areprovided a thermoelectric material and a thermoelectric device, eachincluding the composite.

The thermoelectric material may have good electrical characteristics,and consequentially have improved thermoelectric performance. Thethermoelectric material may be used in a thermoelectric device, athermoelectric module, or a thermoelectric system.

The performance of the thermoelectric material is evaluated using adimensionless figure of merit (ZT), which is defined by Equation 1.

ZT=(S ² σT)/k  Equation 1

In Equation 1, ZT is a figure of merit, S is a Seebeck coefficient, a isan electrical conductivity, T is an absolute temperature, and k is athermal conductivity.

As represented in Equation 1, a higher ZT value of a thermoelectricmaterial may be obtained by increasing the Seebeck coefficient (S) andelectrical conductivity (σ) of the thermoelectric material, i.e., apower factor (S²σ), and reducing the thermal conductivity (k) of thethermoelectric material.

A composite according to any of the above-described embodiments mayinclude graphene, and thus may provide a high electrical conductivityand a low thermal conductivity to a thermoelectric material when usedtherein, due to the characteristics of graphene, and thus improving theperformance of the thermoelectric material.

In a composite according to any of the above-described embodiments,crystalline characteristics and an electron structure may be changed atan interface between metallic graphene and semi-conductive silicon toincrease a Seebeck coefficient thereof and accelerate transfer of chargeparticles, which may consequently induce an increase in electricalconductivity and charge mobility. In addition, phonon scattering at theinterface between the graphene and silicon may be increased, so that itmay be possible to control the thermal conductivity of thermoelectricmaterial.

Such a composite according to any of the above-described embodiments maybe effectively used as a thermoelectric material.

A thermoelectric device may be manufactured by processing thethermoelectric material into a shape, for example, by cutting. Thethermoelectric device may be a p-type thermoelectric device. Thethermoelectric device may be a structure formed by shaping thethermoelectric material in a predetermined shape, for example, inrectangular parallelepiped.

The thermoelectric device may have a cooling effect when combined withan electrode and a current is applied thereto, and have a powergeneration effect due to a temperature difference.

FIG. 3B is a schematic view of a thermoelectric module using thethermoelectric device of FIG. 3E, according to an embodiment of thepresent disclosure. Referring to FIG. 3B, an upper electrode (firstelectrode) 212 and a lower electrode 222 are patterned on an upperinsulating substrate 211 and a lower insulating substrate 221. The upperelectrode 212 and the lower electrode 222 contact a p-typethermoelectric component 215 and an n-type thermoelectric component 316.The upper electrode 212 and the lower electrode 222 are connected to theoutside of the thermoelectric device by a lead electrode 224. The p-typethermoelectric component 215 may be the thermoelectric device accordingto any of the above-described embodiments. The n-type thermoelectriccomponent 316 may not be specifically limited, and may be any materialknown in the art.

The upper and lower insulating substrates 211 and 221 may includegallium arsenic (GaAs), sapphire, silicon, Firex, or quartz. The upperand lower electrodes 212 and 222 may include copper, aluminum, nickel,gold, or titanium, and may have various sizes. The upper and lowerelectrodes 212 and 222 may be formed using any suitable patterningmethod, for example, a lift-off semiconductor process, a depositionmethod, or a photolithography technique.

In some embodiments, one of the first and second electrodes 312 and 322in the thermoelectric module may be exposed to a heat source asillustrated in FIGS. 3C and 3D. In some other embodiments, one of thefirst and second electrodes 312 and 322 in the thermoelectric devicemodule may be electrically connected to a power supply source, or to theoutside of the thermoelectric module, for example, an electric device(for example, a battery) that consumes or stores electric power.

In some embodiments, one of the first and second electrodes 312 and 322in the thermoelectric module may be electrically connected to a powersupply source.

One or more embodiments will now be described in further detail withreference to the following examples. However, these examples are onlyfor illustrative purposes and shall not limit the scope of the disclosedembodiments.

EXAMPLES Preparation Example 1: Preparation of Composite

After fumed SiO₂ particles (having an average particle diameter of about15 nm) were put into a reactor, CH₄ was supplied into the reactor atabout 300 standard cubic centimeters per minute (sccm) at about 1atmosphere (atm) for about 30 minutes, and the temperature of thereactor was raised to about 1000° C., followed by thermal treatment atthe same temperature for about 2 hours.

Subsequently, the temperature of the reactor was cooled down to roomtemperature (about 20° C. to about 25° C.) to obtain a composite inwhich particles of SiO_(x) wherein 0<x≤2 was embedded in graphene.

Preparation Example 2: Preparation of Composite

After fumed SiO₂ particles (having an average particle diameter of about15 nm) were put in a reactor, H₂ was supplied into the reactor at about300 sccm at about 1 atm for about 30 minutes, and the temperature of thereactor was raised to about 1000° C.,

After the temperature of the reactor was maintained at about 1000° C.for about 1 hour, CH₄ was supplied into the reactor at about 300 sccm atabout 1 atm for about 30 minutes, followed by thermal treatment at 1000°C. for about 6 hours. Subsequently, nitrogen was supplied into thereactor at about 300 sccm, and the temperature of the reactor was cooleddown to room temperature (about 20 to about 25° C.) to obtain acomposite in which particles of SiO_(x) wherein 0<x≤2 was embedded ingraphene.

Preparation Example 2a: Preparation of Composite

A composite was prepared in the same manner as in Preparation Example 1,except that CH₄ was supplied into the reactor at about 300 sccm at about1 atm for about 10 minutes.

Preparation Example 3: Preparation of Composite

A composite was prepared in the same manner as in Preparation Example 1,except that CH₄ was supplied into the reactor at about 300 sccm at about1 atm for about 60 minutes.

Preparation Example 4: Preparation of Composite

A composite was prepared in the same manner as in Preparation Example 2,except that CH₄ was supplied into the reactor at about 300 sccm at about1 atm for about 60 minutes.

Preparation Example 5: Preparation of Composite

A composite was prepared in the same manner as in Preparation Example 1,except that H₂ was supplied into the reactor at about 300 sccm at about1 atm for about 4 hours after fumed SiO₂ particles (having an averageparticle diameter of about 15 nm) were put into the reactor, followed byraising the temperature of the reactor to about 1000° C.

Preparation Example 6: Preparation of Composite

A composite was prepared in the same manner as in Preparation Example 1,except that H₂ was supplied into the reactor at about 300 sccm at about1 atm for about 10 minutes after fumed SiO₂ particles (having an averageparticle diameter of about 15 nm) were put into the reactor, followed byraising the temperature of the reactor to about 1000° C.

Comparative Preparation Example 1: Preparation of Structure

A structure was prepared in the same manner as in Preparation Example 3,except that a mixed gas of CH₄ and H₂, instead of CH₄ alone, in a ratioof 100 sccm to 200 sccm, was supplied into the reactor.

Comparative Preparation Example 2: Preparation of Structure

A structure was prepared in the same manner as in Preparation Example 1,except that H₂ was supplied into the reactor at about 300 sccm at about1 atm for about 1 minute after fumed SiO₂ particles (having an averageparticle diameter of about 15 nm) were put into the reactor, followed byraising the temperature of the reactor to about 1000° C.

Comparative Preparation Example 3: Preparation of Structure

A structure was prepared in the same manner as in Preparation Example 1,except that H₂ was supplied into the reactor at about 300 sccm at about1 atm for about 5 minutes after fumed SiO₂ particles (having an averageparticle diameter of about 15 nm), followed by raising the temperatureof the reactor to about 1000° C.

Example 1: Preparation of Electrode Material

An electrode material was prepared by mixing a lithium composite oxide(LiNi_(0.5)Co_(0.2)Mn_(0.3)O₂) (hereinafter, also referred to as NCM)and the composite of Preparation Example 1 by using a Nobilta mixer atabout 300 rpm for about 30 minutes. A mixing ratio of the lithiumcomposite oxide and the composite of Preparation Example 1 was about99:1 by weight.

Examples 2-4: Preparation of Electrode Material

Electrode materials were prepared in the same manner as in Example 1,except that the composites of Preparation Examples 2-4, instead of thecomposite of Preparation Example 1, were used, respectively.

Example 5: Preparation of Electrode Material

An electrode material was prepared by mixing an electrode activematerial (SiNANOde, available from Nanosys, U.S.A) including a graphitecore and a silicon oxide nanowire on the graphite core, and thecomposite of Preparation Example 3 by using a Nobilta mixer at about 300rpm for about 30 minutes. A mixing ratio of the electrode activematerial and the composite of Preparation Example 3 was about 99.3:0.7by weight.

Manufacture Example 1: Manufacture of Electrode and Coin Cell

The electrode material of Example 1 was mixed with Super P carbon(Timcal) as a conducting agent, polyvinylidenedifluoride (PVDF) as abinder, and N-methylpyrrolidone as a solvent to prepare a slurry. Amixed ratio of the electrode material of Example 1, Super P, and PVDFwas about 90:6:4 by weight. The slurry was coated on an aluminum (Al)substrate (having a thickness of about 15 μm) by a bar coating method,and dried at about 200° C. under a reduced pressure, followed by rollpressing and punching to manufacture an electrode. The electrode wasassembled with a lithium metal as a counter electrode, and anelectrolyte to manufacture a coin cell.

The electrode had a capacity of about 1.7 mAh/cm² and a thickness ofabout 55 mm. The electrolyte solution included 1.3M LiPF₆ and EC, DEC,and EMC in a ratio of 3:5:2 by volume.

Manufacture Examples 2-4: Manufacture of Electrode and Coin Cell

Electrodes and coin cells were manufactured in the same manner as inManufacture Example 1, except that the electrode materials of Examples2-4, instead of the electrode material of Example 1, were used,respectively.

Manufacture Example 5: Manufacture of Electrode and Coin Cell

An electrode and a coin cell were manufactured in the same manner as inManufacture Example 1, except that the mixing ratio of the electrodematerial, Super P, and PVDF was changed from about 90:6:4 by weight toabout 97:1.5:1.5 by weight.

Manufacture Example 6: Manufacture of Electrode and Coin Cell

88 parts by weight of the electrode material of Example 5 was mixed with12 parts by weight of lithium polyacrylate (LiPAA), andN-methylpyrrolidone as a solvent to prepare a slurry.

The slurry was coated on an aluminum (Al) substrate (having a thicknessof about 15 μm) by a bar coating method, and dried at about 200° C.under a reduced pressure, followed by roll pressing and punching tomanufacture an electrode. The electrode was assembled with a lithiummetal as a counter electrode, and an electrolyte) to manufacture a coincell.

The cathode had a capacity of about 1.7 mAh/cm² and a thickness of about55 mm. The electrolyte solution included 1.3M LiPF₆ and EC, DEC, and EMCin a ratio of 3:5:2 by volume.

Comparative Manufacture Example 1: Manufacture of Electrode and CoinCell

An electrode and a coin cell were manufactured in the same manner as inManufacture Example 1, except that the structure of ComparativePreparation Example 1, instead of the electrode material of Example 1,was used.

Comparative Manufacture Example 2: Manufacture of Electrode and CoinCell

An electrode and a coin cell were manufactured in the same manner as inManufacture Example 1, except that NCM, instead of the electrodematerial of Example 1, was used.

Comparative Manufacture Example 3: Manufacture of Electrode and CoinCell

An electrode and a coin cell were manufactured in the same manner as inComparative Manufacture Example 2, except that the mixing ratio of NCM,Super P, and PVDF was changed from about 90:6:4 by weight to about97:1.5:1.5 by weight.

Comparative Manufacture Example 4: Manufacture of Electrode and CoinCell

An electrode and a coin cell were manufactured in the same manner as inManufacture Example 1, except that an electrode active material(SiNANOde, available from Nanosys, U.S.A) including a graphite core anda silicon oxide nanowire on the graphite core, was used, instead of theelectrode material of Example 5.

Comparative Manufacture Example 5: Manufacture of Electrode and CoinCell

An electrode and a coin cell were manufactured in the same manner as inManufacture Example 1, except that an electrode material prepared by thefollowing process, instead of the electrode material of Example 5.

The electrode material was prepared by blending an electrode activematerial (SiNANOde, available from Nanosys, U.S.A) including a graphitecore and a silicon oxide nanowire on the graphite core, and thecomposite of Preparation Example 3. A mixing ratio of the electrodeactive material and the composite of Preparation Example 3 was about99.3:0.7 by weight.

Here, the mixing ratio of the electrode active material and thecomposite was about 99:1.

Evaluation Example 1: Specific Surface Area and ConductivityCharacteristics 1) Preparation Examples 1-4 and Comparative PreparationExample 1

Specific surface areas and conductivities of the composites ofPreparation Examples 1 to 4 and the structure of Comparative PreparationExample 1 were evaluated. The results are shown in Table 1. Theconductivity of each sample was evaluated by measuring a resistancewhile scanning at a bias voltage of about 10 millivolts (mV) in afrequency range of 1 hertz (Hz) to 1 MHz.

TABLE 1 Specific surface area Conductivity Example (m²/g) (S/cm)Preparation Example 1 108.3 22.6 Preparation Example 2 104.0 30.1Preparation Example 3 81.9 48.4 Preparation Example 4 83.8 52.1Comparative Preparation 147.1 5.8 Example 1

Referring to Table 1, the composites of Preparation Examples 1 to 4 werefound to have smaller specific surface areas and markedly increasedconductivities, compared to the structure of Comparative PreparationExample 1.

2) Example 4

A specific surface area and conductivity of the electrode material ofExample 4 were evaluated in the same manner as for the composites ofPreparation Examples 1 to 4 and the structure of Comparative PreparationExample 1 as described above. The results are shown in Table 2. Forcomparison, a specific surface area and a conductivity of NCM are alsorepresented in Table 2.

TABLE 2 Specific surface area Conductivity Example (m²/g) (S/cm) Example4 14.4 3.54 × 10⁻² NCM 7.4 4.17 × 10⁻³

Referring to Table 2, the electrode material of Example 4 was found tohave an improved conductivity, compared to NCM.

3) Example 5

A conductivity of the electrode material of Example 5 was evaluated inthe same manner as for the composites of Preparation Examples 1 to 4 andthe structure of Comparative Preparation Example 1 as described above.The results are shown in Table 3. For comparison, a conductivity of theanode active material (hereinafter, referred to as “electrode activematerial A”) used as a starting material to prepare the electrodematerial of Example 5, the electrode active material A including agraphite core and a silicon oxide nanowire on the graphite core, is alsorepresented.

TABLE 3 Example conductivity (S/cm) Example 5 44.5 Electrode activematerial A 6.37

Referring to Table 3, the electrode material of Example 5 was found tohave an improved conductivity, compared to the electrode active materialA.

Evaluation Example 2: Scanning Electron Microscopy (SEM) andHigh-Resolution Transmission Electron Microscopy (HR-TEM) 1) PreparationExamples 3 and 5

Silicon oxide (SiO₂) and the composites of Preparation Examples 3 and 5were analyzed by scanning electron microscopy (SEM) and high-resolutiontransmission electron microscopy (HR-TEM).

The SEM analysis was performed using an ultrahigh-resolution scanningelectron microscope (UHR-FE-SEM, Hitachi S-5500, Resolution; 0.4 nm) (at30 kV), and the TEM analysis was performed using a Tecnai Titan(available from FEI). The results are shown in FIGS. 4A to 4H.

FIGS. 4A and 4B are HR-TEM images of the composite of PreparationExample 3. FIGS. 4C and 4D are SEM images of the composite ofPreparation Example 3.

FIGS. 4E and 4F are HR-TEM and SEM images of the composite ofPreparation Example 5, respectively. FIGS. 4G and 4H are HR-TEM and SEMimages of silicon oxide (SiO₂), respectively.

Referring to FIGS. 4A to 4F, the composites of Preparation Example 3(Time taken to raise temperature to a heat treatment temperature of1000° C., hereinafter, also referred to as “reaction time”): about 60min, and Preparation Example 5 (reaction time: about 4 hours) were foundto include SiO_(x) wherein 0<x≤2 embedded in graphene. The SiO_(x)wherein 0<x≤2 had an average particle diameter of about 15 nm, and wasuniformly distributed in graphene. The composites of PreparationExamples 3 and 4 had a particle diameter of about 100 nm to about 200nm. The SiO_(x) wherein 0<x≤2 was uniformly dispersed in the graphene.

2) Example 1

The electrode material of Example 1 was analyzed by SEM and HR-TEM inthe same manner as for the composites of Preparation Examples 3 and 5 asdescribed above. The results are shown in FIGS. 5A to 5F. Forcomparison, the results of SEM and HR-TEM on NCM are also represented inFIGS. 5G and 5H, respectively.

FIGS. 5B and 5H are magnified views of the SEM images of FIGS. 5A and5G, respectively.

FIGS. 5C to 5F are HR-TEM images of the electrode material of Example 1.

FIGS. 5D and 5F are magnified views of the HR-TEM images of FIGS. 5C and5E, respectively.

Referring to FIGS. 5A to 5H, surface pores of NCM appear filled withgraphene composite, and the surface of NCM was coated with graphene. Dueto this structure, the graphene in the electrode material of Example 1may suppress a side reaction in the cathode and prevent a reduction inconductivity.

3) Example 6

The electrode material of Example 6 was analyzed by HR-HEM in the samemanner as for the composites of Preparation Examples 3 and 4.

The results are shown in FIGS. 51 to 5K. For comparison, silicon oxideused as a starting material to prepare the electrode material of Example6 was analyzed by HR-TEM. The results are shown in FIGS. 5L and 5M.

Referring to FIGS. 5L to 5M, the electrode material of Example 6 wasfound to include a graphene layer formed on silicon oxide particles.

Evaluation Example 3: Charge-Discharge Characteristics

(1) Evaluation of Initial Efficiency, Rate Capability, CoulombEfficiency, and Discharge Capacity

1) Manufacture Example 1 and Comparative Manufacture Example 2

Charge and discharge characteristics of the coin cells of ManufactureExample 1 and Comparative Manufacture Example 2 were evaluated.

Each of the coin cells of Manufacture Example 1 and ComparativeManufacture Example 2 was subjected to one cycle of charging anddischarging at 0.1 C rate (formation process), followed by one cycle ofcharging and discharging at 0.2 C and then initial charge-dischargecharacteristic measurement. After further 50 cycles of charging anddischarging at 1 C rate, cycle characteristics of the coin cell wereevaluated. In particular, the charging was set to begin with a constantcurrent (CC) mode and shift to a constant voltage (CV) mode to terminateat a cut-off of 0.01 C, and the discharging was set to terminate at aconstant current mode in a voltage range of Table 4.

The cycle characteristics were repeatedly measured up to about the100^(th) cycle at which the specific capacity is reduced to about 92% ofa 1^(st) cycle specific capacity, while controlling a current to beabout 50 mA per 1 g of the electrode.

Discharge rate characteristics of the coin cells were evaluated aftercharging and discharging at 0.05 C/0.5 C. The results are shown in Table4. A change in discharge capacity of the coin cells of ManufactureExample 1 and Comparative Manufacture Example 2 with respect to thenumber of cycles was measured. The results are shown in FIGS. 6A and 6Band Table 5. In FIGS. 6A and 6B, “bare NCM” denotes the coin cell ofComparative Manufacture Example 2, and “SiO₂@Gr.NCM” denotes the coincell of Manufacture Example 1.

TABLE 4 1^(st) cycle 0.05 C- Discharge Initial Rate capability Cut-offvoltage capacity efficiency (%) Coulombic Lifetime Example (V) (mAh/g)(%) 0.5 C/0.05 C efficiency (%) (%@100^(th)) Manufacture Example 1 4.4198.3 93.71 92.72 99.96 99.98 Comparative 4.4 198.5 92.49 92.72 99.7598.16 Manufacture Example 2 Manufacture Example 1 4.5 208.5 92.89 93.5599.90 97.32 Comparative 4.5 209.3 91.95 91.64 99.63 91.83 ManufactureExample 2

Referring to Table 4, the coin cell of Manufacture Example 1 was foundto have improved initial efficiency and improved lifetimecharacteristics, compared to the coin cells of Comparative ManufactureExample 2.

2) Manufacture Example 5 and Comparative Manufacture Example 3

Charge and discharge characteristics of the coin cells of ManufactureExample 5 and Comparative Manufacture Example 3 were evaluated in thesame manner as for the coin cells of Manufacture Example 1 andComparative Manufacture Example 2 as described above. The results areshown in FIGS. 6C and 6D.

In FIGS. 6C and 6D, “Bare” denotes the coin cell of ComparativeManufacture Example 3, and “G@SiO₂” denotes the coin cell of ManufactureExample 5.

The initial efficiency, rate capability, and lifetime characteristics ofeach of the coin cells were calculated using Equations 1, 2, and 3,respectively.

Initial efficiency={(1^(st) cycle discharge capacity)/(1^(st) cyclecharge capacity)}×100  Equation 1

Rate capability={(0.5C discharge capacity)/(0.05C dischargecapacity)}×100  Equation 2

Lifetime={(100^(th) cycle discharge capacity)/(1^(st) cycle dischargecapacity)}×100  Equation 3

TABLE 5 1^(st) cycle 0.05 C- Discharge Initial Rate Coulombic Cut-offcapacity efficiency capability (%) efficiency Lifetime Example voltage(V) (mAh/g) (%) 0.5 C/0.05 C (%) % (% @100^(th)) Manufacture 4.4 198.894.11 92.34 99.92 95.41 Example 5 Comparative 4.4 199.3 93.07 90.93 99.884.42 Manufacture Example 3 Manufacture 4.5 212.3 93.13 93.00 99.7586.73 Example 5 Comparative 4.5 211.1 92.31 91.64 99.70 77.82Manufacture Example 3

Referring to Table 5 and FIGS. 6C and 6D, the Coin Cell of Manufacture

Example 5 was found to have an improved initial efficiency and improvedresistance against high voltage, compared to the coin cell ofComparative Manufacture Example 3. This is attributed to the suppressionof side reaction due to the use of the electrode material including thecomposite of Example 1 coated on the surface of NCM.

3) Manufacture Example 6, Comparative Manufacture Example 4

Charge and discharge characteristics of the coin cells of ManufactureExample 6 and Comparative Manufacture Example 4 were evaluated in thesame manner as described above.

The results are shown in FIG. 6E and Table 6. In FIG. 6E, “16Nsys”denotes the coin cell of Comparative Manufacture Example 4, and“S.S.SiO₂@Gr.-16Nsys” denotes the coin cell of Manufacture Example 6.

TABLE 6 1^(st) cycle 0.1 C- Discharge Initial capacity efficiency Ratecapability (%) Lifetime Example (mAh/g) (%) 0.5 C/0.05 C (%@100^(th))Manufacture 781.5 87.82 96.16 80.07 Example 6 Comparative 772.9 87.489.24 74.04 Manufacture Example 4

Referring to Table 6, the coin cell of Manufacture Example 6 was foundto have improved charge and discharge characteristics and improvedlifetime characteristics, compared to the coin cell of ComparativeManufacture Example 4.

(2) Rate Capability

1) Manufacture Example 1 and Comparative Manufacture Example 2

Rate capabilities of the coin cells of Manufacture Example 1 andComparative Manufacture Example 2 were evaluated at different rates asfollows.

A charge and discharge test was performed on coin cell of ManufactureExample 1) at a low rate of 0.05 C/0.05 C to evaluate a capacity, and ata rate of 0.5 C/0.05 C to evaluate rate characteristics according to thefollowing equation. For comparison, the charge and discharge test wasperformed on the coin cells of Comparative Manufacture Example 2 underthe same conditions.

Rate capability={(0.5C Discharge capacity)/(0.05C Dischargecapacity)}×100

The results of the rate characteristics evaluation are shown in Table 7and FIG. 6F. In FIG. 6F, “Bare NCM” denotes the coin cell of ComparativeManufacture Example 2, and “SiO₂@Gr.-NCM” denotes the coin cell ofManufacture Example 1.

TABLE 7 Comparative Manufacture Example 2 Charge and Manufacture Example1 Degree of improvement (Δ) discharge Charge and Charge and Dischargerate Capacity efficiency Capacity discharge Capacity discharge (C rate)(mAh/g) (%) (mAh/g) efficiency (%) (mAh/g) efficiency (%) 0.05 198.392.43 197.1 93.16 −1.28 0.73 0.1 194.5 97.62 194.9 97.67 0.4 0.05 0.2189.8 97.19 192.2 98.10 2.4 0.91 0.5 182.0 95.57 184.8 96.07 2.8 0.5 1175.1 95.99 177.4 96.09 2.3 0.1

Referring to Table 7 and FIG. 6F, the coin cell of Manufacture Example 1was found to have improved rate characteristics, compared to the coincell of Comparative Manufacture Example 2.

2) Manufacture Example 5 and Comparative Manufacture Example 3

Rate capabilities of the coin cells of Manufacture Example 5 andComparative Manufacture Example 3 were evaluated in the same manner asfor the coin cells of Manufacture Example 1 and Comparative ManufactureExample 2 as described above.

The results of the rate characteristics evaluation were shown in Table 8and FIG. 6G. In FIG. 6G, “Bare NCM” denotes the coin cell of ComparativeManufacture Example 3, and “SiO₂@Gr.-NCM” denotes the coin cell ofManufacture Example 5.

TABLE 8 Comparative Manufacture Example 3 Charge and Manufacture Example5 Degree of improvement (Δ) discharge Charge and Charge and Dischargerate Capacity efficiency Capacity discharge Capacity discharge (C rate)(mAh/g) (%) (mAh/g) efficiency (%) (mAh/g) efficiency (%) 0.05 198.692.8 196.8 93.9 −1.8 1.1 0.1 195.1 97.5 193.9 97.6 −1.2 0.1 0.2 191.297.6 191.2 98.2 0 0.6 0.5 183.1 95.6 183.9 96.2 1 0.6 1 173.3 94.5 175.995.9 2.7 1.4 2 125.1 72.2 135.6 77.3 10.5 5.1

Referring to Table 8 and FIG. 6G, the coin cell of Manufacture Example 5was found to have improved rate characteristics, compared to the coincell of Comparative Manufacture Example 3.

3) Manufacture Example 6, and Comparative Manufacture Examples 4 and 5

Rate capabilities of the coin cells of Manufacture Example 6 andComparative Manufacture Examples 4 and 5 were evaluated in the samemanner as for the coin cells of Manufacture Example 1 and ComparativeManufacture Example 2 as described above.

The results are shown in Table 9. A cut-off voltage was in a range ofabout 4.4 V.

TABLE 9 Example Rate capability (%) Manufacture Example 6 96.16Comparative Manufacture 91.71 Example 4 Comparative Manufacture 89.24Example 5

Referring to Table 9, the coin cells of Manufacture Example 6 was foundto have improved rate characteristics, compared to the coin cell ofComparative Manufacture Examples 4 and 5.

Evaluation Example 3: X-Ray Photoelectron Spectroscopy (XPS) 1)Preparation Example 4 and Example 4

The composite of Preparation Example 4 and the electrode material ofExample 4 were analyzed by X-ray photoelectron spectroscopy (XPS) usinga Quantum 2000 (available from Physical Electronics). The results of theXPS analysis are shown in FIG. 7A. For comparison, the results of XPS onlithium composite oxide (LiNi_(0.5)Co_(0.2)Mn_(0.3)O₂) (NCM) are alsorepresented. In FIG. 7A, “SiO₂@Gr” denotes the composite of PreparationExample 4, and “SiO₂@Gr-NCM” denotes the electrode material of Example4.

The results of compositional XPS analysis on the composite ofPreparation Example 4 and the electrode material of Example 4 are shownin Table 10.

TABLE 10 Amount of carbon Amount of oxygen Amount of siliconcorresponding to corresponding to corresponding to C 1 s peak O 1 s peakSi 2 p peak Example (Atomic %) (Atomic %) (Atomic %) Preparation 98.661.08 0.25 Example 4 Example 4 52.97 43.86 3.16 NCM 29.39 69.16 0

Referring to FIG. 7A and Table 10, the composite of Preparation Example4 and the electrode material of Example 4 were found to have features ofgraphene, which was clear from the spectrum of C is.

2) Preparation Examples 1, 3 and 5, and Comparative Preparation Examples2 and 3

The composites of Preparation Examples 1, 3 and 5 and the structures ofComparative Preparation Examples 2 and 3 were analyzed by XPS using aQuantum 2000 (available from Physical Electronics) with a beam size ofabout 100 μm. The results are shown in FIGS. 7B to 7E.

In FIG. 7B, a, b, c, d, and e indicate the times taken to raisetemperature to a heat treatment temperature of about 1000° C., i.e.,about 4 hours (Preparation Example 5), 60 minutes (Preparation Example3), 30 minutes (Preparation Example 1), 5 minutes (ComparativePreparation Example 3), and 1 minute (Comparative Preparation Example2), respectively, and f denotes the sample (fumed SiO₂ particles) beforethe thermal treatment. FIGS. 7C to 7E illustrate XPS spectra of C 1s, O1s, and Si 2p, respectively, of the composites of Preparation Examples1, 3 and 4 and the structures of Comparative Preparation Examples 2 and3. The C is peak (a binding energy of about 284.48 eV) was used as peakreference.

Referring to FIGS. 7B to 7E, in the composites of Preparation Examples1, 4, and 5 in which it took 30 minutes or longer to raise temperatureto 1000□, graphene was detected as major component with almost nosilicon oxide (SiO₂) component. FIG. 7F illustrates XPS valence bandspectra of the composites of Preparation Examples 1, 3 and 5, thestructures of Comparative Preparation Examples 2 and 3, and siliconoxide (SiO₂) as a starting material.

The results of compositional XPS analysis on the composites ofPreparation Example 1, 3, and 5, the structures of ComparativePreparation Examples 2 and 3, and silicon oxide (SiO₂) as a startingmaterial are shown in Table 11.

TABLE 11 Amount of Amount of Amount of carbon cor- oxygen cor- siliconcor- responding responding responding Reaction time to C 1 to O 1 to Si2 (Temperature s peak s peak p peak Example increase time) (Atomic %)(Atomic %) (Atomic %) Preparation 30 min 96.24 2.11 1.65 Example 1Preparation 60 min 99.06 0.8 0.15 Example 3 Preparation 4 hr 97.64 1.710.65 Example 5 Comparative 1 min 9.5 51.33 39.17 Preparation Example 2Comparative 5 min 10.47 50.57 38.97 Preparation Example 3 SiO₂ 0 min8.62 53.54 37.64

Referring to Table 11, the structures of Comparative PreparationExamples 2 and 3 in which the reaction time was about 5 min or werefound to include SiO₂ as major component, while the composites ofPreparation Examples 1, 3, and 5 in which the reaction time was about 30min or longer were found to include graphene as major component.

Referring to FIGS. 7B to 7E, it was found that peak shifting occurred asthe reaction time increased, indicating generation of a reductionproduct of silicon oxide (SiO₂) used as a starting material.

Referring to FIG. 7F, only a valence-band structure of SiO₂ was observedin the XPS valence band spectra of the structures of ComparativePreparation Examples 2 and 3 in which the reaction time was about 5 minor less, while a valence-band structure of graphene was observed in theXPS valence band spectra of the composites of Preparation Examples 1, 3,and 5 in which the reaction time was 30 min or longer to.

Uniformities of carbon and silicon over different regions were analyzedbased on the results in Table 11. The results are shown in Table 12.

The uniformity of carbon and silicon in each sample was obtained as adeviation in the amounts of carbon and silicon in 10 regions of thesample from an average amount of carbon and silicon obtained based onXPS analysis results.

TABLE 12 Example Uniformity (%) Preparation Example 1  1% PreparationExample 3 0.98 Preparation Example 5 0.99%  Comparative PreparationExample 2 5.1% Comparative Preparation Example 3 5.5% SiO₂ 5.0%

Referring to Table 12, the composites of Preparation Example 1, 3, and 5were found to have an improved uniformity of 1% or less, compared to thestructures of Comparative Preparation Examples 2 and 3 and SiO₂.

3) Preparation Example 3 and Example 5

The composite of Preparation Example 3 and the electrode material ofExample 5 were analyzed by XPS in the same manner as for the compositeof Preparation Example 4 and Example 4 as described above. Forcomparison, XPS data of electrode active material A that was used as astarting material to prepare the electrode material of Example 5 wasalso represented.

The results of compositional XPS analysis on the samples are shown inTable 13 and FIGS. 7G and 7H. In FIGS. 7G and 7H, “SiO₂@Gr” indicatesthe composite of Preparation Example 3, “SiO₂@Gr.-16Nsys” indicates theelectrode material of Example 5, and “16 Nsys” indicates the electrodeactive material A.

TABLE 13 Amount of oxygen Amount of silicon Amount of carboncorresponding to corresponding to corresponding to O 1 s peak Si 2 ppeak Example C 1 s peak (Atomic %) (Atomic %) Preparation 98.66 1.080.25 Example 3 Example 5 67.36 20.97 11.67 electrode 2.32 69.18 28.51active material A

Evaluation Example 4: Scanning Electron Microscopy with EnergyDispersive Analysis of X-rays (SEM-EDAX)

The electrode material of Example 1 was analyzed by scanning electronmicroscopy combined with energy dispersive analysis of X-rays (SEM-EDAX)using a FEI Titan 80-300 (available from Philips). The results of theSEM-EDAX are shown in FIGS. 8A to 8H.

Referring to FIGS. 8A to 8H, the electrode material of Example 1 wasfound to include the composite of Preparation Example 1 coating thesurface of NCM. FIGS. 8A and 8E are the results of the SEM-EDAX on theentire electrode material of Example 1. FIGS. 8B and 8F are the resultsof SEM-EDAX on nickel, FIGS. 8C and 8G are the results of SEM-EDAX oncarbon, and FIGS. 8E and 8H are the results of SEM-EDAX on silicon.

Evaluation Example 5: Thermogravimetric Analysis 1) Preparation Examples1 and 4 and Comparative Preparation Examples 1 to 3

The composites of Preparation Examples 1 to 4 and the structures ofComparative Preparation Examples 1 to 3) were analyzed bythermogravimetry using a thermogravimetric analyzer (SDF-2960, availablefrom TA instrument). The resulting thermogravimetricanalysis-differential thermogravimetric analysis (TGA-DTGA) curvesthereof are shown in FIG. 9A. For comparison, the results of TGA onfumed SiO₂ particles used as a starting material in Preparation Examples1 to 4 are also represented in FIG. 9A. In FIG. 9A, “30 m CH₄ all”denotes the composite of Preparation Example 1, “30 m CH₄—H₂” denotesthe composite of Preparation Example 2, “60 m CH₄ all” denotes thecomposite of Preparation Example 3, “60 m CH₄—H₂” denotes the compositeof Preparation Example 4, and “30 m Conv.-CVD” denotes the structure ofComparative Preparation Example 1. The amount of graphene in each of thesamples was calculated based on the results in FIG. 9A, and is shown inTable 14.

TABLE 14 Example Amount of graphene (wt %) Preparation Example 1 42.5Preparation Example 2 46.1 Preparation Example 3 56.2 PreparationExample 4 69.5 Comparative Preparation Example 1 17.1 ComparativePreparation Example 2 2 Comparative Preparation Example 3 10

Referring to FIG. 9A and Table 14, the composites of PreparationExamples 1 to 4 were found to contain relatively large amount ofgraphene due to the active growth of graphene, compared to thestructures of Comparative Preparation Examples 1 to 3.

2) Example 4 and NCM

The electrode material of Example 4 and NCM were analyzed bythermogravimetry in the same manner as for the composites of PreparationExamples 1 to 4 and the structure of Comparative Preparation Example 1as described above.

The results of the TGA are shown in FIG. 9B and Table 15. In FIG. 9B,“NCM” indicates a lithium composite oxide(LiNi_(0.5)Co_(0.2)Mn_(0.3)O₂), and “SiO₂@Gr-NCM” indicates thecomposite of Example 4.

TABLE 15 Example Amount of graphene (wt %) Preparation Example 4 58.9Example 4 0.3 NCM 0

Evaluation Example 6: X-Ray Diffraction Analysis 1) Preparation Examples1-4 and Comparative Preparation Example 1

The composites of Preparation Examples 1 to 4 and the structure ofComparative Preparation Example 1 were analyzed by X-ray diffractionanalysis with CuKα radiation.

The results of the X-ray diffraction analysis are shown in FIG. 10A. InFIG. 10A, “30 m CH₄ all” denotes the composite of Preparation Example 1,“30 m CH₄—H₂” denotes the composite of Preparation Example 2, “60 m CH₄all” denotes the composite of Preparation Example 3, and “60 m CH₄—H₂”denotes the composite of Preparation Example 4, denotes the structure ofComparative Preparation Example 1.

Referring to FIG. 10A, in the composites of Preparation Examples 1 to 4,peak shifting occurred due to the inclusion of a reproduction product ofsilicon oxide (SiO²), compared to the SiO₂.

2) Preparation Examples 1, 3 and 5, and Comparative Preparation Examples2 and 3

The composites of Preparation Examples 1, 3, 5 and the structures ofComparative Preparation Examples 2 and 3 were analyzed by X-raydiffraction analysis with CuKα radiation.

The results of the X-ray diffraction analysis are shown in FIG. 10B. InFIG. 10B, “SiO₂—0 min” denotes silicon oxide (SiO₂), “1 min” denotes thestructure of Comparative Preparation Example 2, “5 min” denotes thestructure of Comparative Preparation Example 3, “30 min” denotes thecomposite of Preparation Example 1, “60 min” denotes the composite ofPreparation Example 3, and “4 hrs” denotes the composite of PreparationExample 5.

Evaluation Example 7: Raman Spectroscopy 1) Preparation Examples 1-4

The composites of Preparation Examples 1 to 4 were analyzed by Ramanspectroscopy.

The results of the Raman spectroscopy are shown in FIG. 11A. In FIG.11A, “30 m CH₄ all” denotes the composite of Preparation Example 1, “30m CH₄—H₂” denotes the composite of Preparation Example 2, “60 m CH₄ all”denotes the composite of Preparation Example 3, and “60 m CH₄—H₂”denotes the composite of Preparation Example 4.

An intensity ratio of D peak to G peak (D/G) of each of the compositeswas obtained based on the results of FIG. 11A. The results are shown inTable 16.

A Raman spectrum of graphene includes peaks at 1350 cm⁻¹, 1580 cm⁻¹, and2700 cm⁻¹, which give information about the thickness, crystallinity,and charge doping status of the graphene. The peak at 1580 cm⁻¹, whichis a peak called G-mode, results from a vibrational mode of C—C bondstretching. The energy of G-mode is determined depending on the densityof surplus charges. The peak at 2700 cm⁻¹, which is a peak called2D-mode, indicates the thickness of graphene. The peak at 1350 cm⁻¹,which is a peak called D-mode, indicates that a SP² crystal structureincludes a defect. The intensity ratio of D/G indicates the degree ofdisordering of graphene crystals.

TABLE 16 Example Intensity ratio of D/G Preparation Example 1 1.076Preparation Example 2 1.055 Preparation Example 3 1.068 PreparationExample 4 1.093

Referring to 11a and Table 16, in consideration of the intensity ratioof D/G of graphene, it was found that the quality of graphene did notdegrade even when the amount of graphene increases as the reaction timeincreases.

2) Preparation Example 4 and Example 4

The composite of Preparation Example 4 and the electrode material ofExample 4 were analyzed by Raman spectroscopy in the same manner as forthe composites of Preparation Examples 1 to 4. For comparison, a Ramanspectrum of NCM was also represented.

The results of the Raman spectroscopy are shown in FIG. 11B and Table17. In FIG. 11B, “SiO₂@Gr.” denotes the composite of Preparation Example4, “SiO₂@Gr.-NCM” denotes the electrode material of Example 4, and “BareNCM” denotes lithium composite oxide (LiNi_(0.5)Co_(0.2)Mn_(0.3)O₂).

TABLE 17 Example Intensity ratio of D/G Preparation Example 4 1.093Example 4 1.146

3) Preparation Examples 1, 3, and 5, Comparative Preparation Examples 2and 3

The composites of Preparation Examples 1, 3, and 5 and the structures ofComparative Preparation Examples 2 and 3 were analyzed by Ramanspectroscopy in the same manner as for the composites of PreparationExamples 1 to 4.

The results of the Raman spectroscopy are shown in FIG. 11C and Table18. In FIG. 11C, “1 min” denotes the structure of ComparativePreparation Example 2, “5 min” denotes the structure of ComparativePreparation Example 3, “30 min” denotes the composite of PreparationExample 1, “60 min” denotes the composite of Preparation Example 3, and“4 hrs” denotes the composite of Preparation Example 5.

TABLE 18 Example Intensity ratio of D/G Preparation Example 1 1.2Preparation Example 3 1.2 Preparation Example 5 1.3 ComparativePreparation 1.6 Example 2 Comparative Preparation 1.2 Example 3

Referring to Table 18, when the reaction time was 5 minutes or longer(Preparation Examples 1, 3, and 5), the intensity ratios of D/G were notsignificantly different, unlike when the reaction time was shorter than5 minutes (Comparative Preparation Examples 2 and 3).

4) Preparation Example 3 and Example 5

The composite of Preparation Example 3 and the electrode material ofExample 5 were analyzed by Raman spectroscopy in the same manner asdescribed above.

The results of the Raman spectroscopy are shown in FIG. 11D and Table19. In FIG. 11D, “16Nys” denotes a starting material, that is, anelectrode active material (SiNANOde, available from Nanosys, U.S.A)including a graphite core and a silicon oxide nanowire on the graphitecore used to prepare the electrode material of Example 5,“SiO₂@Gr-16Nys” denotes the electrode material of Example 5, and“SiO₂@Gr” denotes the composite of Preparation Example 3.

TABLE 19 Example Intensity ratio of D/G Preparation Example 3 1.093Example 5 1.146

Evaluation Example 8: Adhesion Test 1) Example 4

The adhesions of the electrode material of Example 4 and NCM were testedaccording to a T-peel a test (ASTM D1876). The results of the adhesiontest are shown in Table 20.

TABLE 20 Example Adhesion (N/m) Example 4 121.31 NCM 118.24

Referring to Table 20, the electrode material of Example 4 was found tohave improved adhesion, compared to NCM.

2) Example 5

The adhesion of the electrode material of Example 1 was tested in thesame manner as for the electrode material of Example 4. The results areshown in Table 21. For comparison, the adhesion of the starting material(i.e., the electrode active material (hereinafter referred to aselectrode active material A) including a graphite core and a siliconoxide nanowire on the graphite core) used to prepare the electrodematerial of Example 5 is also represented in Table 21.

TABLE 21 Example Adhesion (N/m) Example 5 27.43 Electrode activematerial A 2.71

Referring to Table 21, the electrode material of Example 5 was found tohave improved adhesion, compared to the electrode active material A.

Evaluation Example 9: 29Si{¹H}-Cross-Polarization/Magic-Angle SpinningNuclear Magnetic Resonance (CP/MAS NMR) Spectroscopy

The composite of Preparation Example 5, the structure of ComparativePreparation Example 2, and SiO₂ were analyzed by 29Si{¹H}-CP/MAS NMRspectroscopy, which was performed at a spinning rate of about 5 kHzusing a Bruker 700 MHz NMR spectrometer with rotors in which about 100mg to 200 mg of samples were loaded. The results are shown in FIG. 12.In FIG. 12, “SiO₂-4 hrs” denotes the composite of Preparation Example 5,and “SiO₂—1 min” denotes the structure of Comparative PreparationExample 2.

Referring to FIG. 12, the composite of Preparation Example 5 “SiO₂-4hrs” was found to have Si-O-related peaks that became broad in width andlower in peak intensity, with the increase of time, compared to thestructure of Comparative Preparation Example 2 and SiO₂, indicating thatthe composite of Preparation Example 5 loses characteristics of SiO₂that appears in the structure of Comparative Preparation Example 2 andSiO₂.

Evaluation Example 10: Transmission Electron Microscopy withEnergy-Dispersive X-ray Spectrometry (TEM-EDS) 1) Preparation Example 6

The composite of Preparation Example 6 was analyzed by transmissionelectron microscopy with energy-dispersive X-ray spectrometry (TEM-EDS)using an analysis equipment including a transmission electron microscopewith an energy-dispersive X-ray spectrometer attached. As a result,high-angle annular dark field scanning transmission electron microscopic(HAADF-STEM) images of the composite of Preparation Example 6 wereobtained, and qualitative analysis was performed on component elements.For comparison, silicon oxide (SiO₂) used as a starting material toprepare the composite of Preparation Example 6 was also analyzed byTEM-EDS. A HAADF-STEM image of the composite of Preparation Example 6 isshown in FIG. 13A. A carbon map, silicon-carbon map overlap, siliconmap, oxygen map, and silicon and oxygen map overlap of the composite ofPreparation Example 6 are shown in FIGS. 13B to 13F, respectively. Theresults of the TEM-EDS on the silicon oxide (SiO₂) are shown in FIGS.13G to 13K.

Referring to FIG. 13A, the composite of Preparation Example 6 was foundto have a uniform distribution of Si-O. As shown in FIG. 13C, thecomposite of Preparation Example 6 was found to include graphene regions(delimited by circles) grown around the at least one selected fromsilicon oxide (SiO₂) and a reduction product thereof (SiO_(x)) (where0<x<2) particles and to include oxygen in the graphene regions,indicating that the at least one selected from silicon oxide (SiO₂) anda reduction product thereof (SiO_(x)) (where 0<x<2) is distributed ingraphene.

2) Preparation Example 1

The composite of Preparation Example 1 was analyzed by TEM-EDS in thesame manner as for the composite of Preparation Example 6.

The results are shown in FIGS. 15A to 15C. TEM images of the compositesof Preparation Example 1 are shown in FIGS. 14A to 14D.

FIG. 15B is a silicon map of a region delimited by a rectangular in FIG.15A, obtained from an EDS spectrum of the composite of PreparationExample 1. Referring to FIGS. 15B and 15C, the composite of PreparationExample 1 was found to have uniform distribution of silicon.

3) Preparation Example 3

The composite of Preparation Example 3 was analyzed by TEM-EDS in thesame manner as for the composite of Preparation Example 6. The resultsare shown in FIG. 16. FIG. 16 is a HREM and STEM-HADDF image of thecomposite of Preparation Example 16.

In FIG. 16, the result of component analysis of the composite ofPreparation Example 3, and a degree of dispersion of at least oneselected from silicon oxide (SiO₂) and a reduction product thereof(SiO_(x)) (where 0<x<2) are shown.

As described above, according to the one or more of the aboveembodiments, using a composite according to any of the above-describedembodiments, or an electrochemically active material composite includingthe composite may improve electrode conductivity and efficientlysuppress side reaction between electrochemically active material andelectrolyte. A lithium battery having improved charge and dischargeefficiency may be manufactured using any of the composites orelectrochemically active material composites according to theabove-described embodiments.

It should be understood that the exemplary embodiments described thereinshould be considered in a descriptive sense only and not for purposes oflimitation. Descriptions of features or aspects within each embodimentshould typically be considered as available for other similar featuresor aspects in other embodiments.

While one or more embodiments have been described with reference to thefigures, it will be understood by those of ordinary skill in the artthat various changes in form and details may be made therein withoutdeparting from the spirit and scope as defined by the following claims.

What is claimed is:
 1. An electrochemically active material compositecomprising a composite and an electrochemically active material, whereinthe composite comprises particles comprising a silicon oxide of theformula SiO₂ and a silicon oxide of the formula SiOx wherein 0<x<2; andgraphene, wherein the particles comprising a silicon oxide of theformula SiO₂ and a silicon oxide of the formula SiOx wherein 0<x<2 aresurrounded by the graphene, wherein the amount of the compositecomprising a silicon oxide of the formula SiO₂ and a silicon oxide ofthe formula SiOx wherein 0<x<2; and graphene is in a range of about 0.1parts by weight to less than about 100 parts by weight based on 100parts by weight of the total weight of the composite and theelectrochemically active material.
 2. The electrochemically activematerial composite of claim 1, wherein the amount of the composite is ina range of about 0.5 parts by weight to about 30 parts by weight basedon 100 parts by weight of the total weight of the composite and theelectrochemically active material.
 3. The electrochemically activematerial composite of claim 1, wherein the amount of the composite is ina range of about 0.7 parts by weight to about 1 parts by weight based on100 parts by weight of the total weight of the composite and theelectrochemically active material.
 4. The electrochemically activematerial composite of claim 1, wherein the particles comprising asilicon oxide of the formula SiO₂ and a silicon oxide of the formulaSiOx wherein 0<x<2 are completely surrounded by the graphene, and theparticles comprising a silicon oxide of the formula SiO₂ and a siliconoxide of the formula SiOx wherein 0<x<2 completely surrounded by thegraphene are interconnected with each other in a graphene matrix.
 5. Theelectrochemically active material composite of claim 1, wherein anamount of the graphene in the composite is in a range of about 0.001parts by weight to about 90 parts by weight, based on 100 parts byweight of the composite.
 6. The electrochemically active materialcomposite of claim 1, wherein the graphene is oriented at an angle ofabout 0° to about 90°, with respect to a surfaceprimary axis of asilicon oxide of the formula SiO₂ and a silicon oxide of the formulaSiOx wherein 0<x<2.
 7. The electrochemically active material compositeof claim 1, wherein the graphene is oriented parallel to a surface ofthe silicon; or the graphene is oriented at an angle of about 3° toabout 85°, with respect to a primary axis of the silicon.
 8. Theelectrochemically active material composite of claim 1, wherein anintensity ratio of D peak to G peak (D/G) in a Raman spectra of thecomposite is about 0.5 to about 1.5.
 9. The electrochemically activematerial composite of claim 1, wherein the graphene has a sphericalstructure having a size of about 50 nanometers to about 300 nanometers.10. The electrochemically active material composite of claim 1, whereinthe silicon oxide of the formula SiO₂ or the silicon oxide of theformula SiOx wherein 0<x<2 has an average particle diameter of about 1nanometers to about 20 nanometers.
 11. The electrochemically activematerial composite of claim 1, wherein the graphene extends from thesilicon oxide by a distance of about 10 nm or less, comprises at leastone to 20 graphene layers, and has a total thickness of about 0.6nanometers to about 12 nanometers.
 12. The electrochemically activematerial composite of claim 1, wherein the composite has specificsurface areas of about 81.9 m²/g to about 108.3 m²/g, and the compositehas a conductivity of about 22.6 S/cm to about 52.1 S/cm.
 13. Theelectrochemically active material composite of claim 1, wherein thegraphene has a branched structure comprising contacting grapheneparticles, and wherein the silicon oxide is distributed in the branchedstructure.
 14. The electrochemically active material composite of claim1, wherein the composite has a faceted-sphere structure or a crumpledpaper ball structure, and the silicon oxide of the formula SiO₂ or thesilicon oxide of the formula SiOx wherein 0<x<2 is distributed in thefaceted-sphere structure or crumpled paper ball structure.
 15. Theelectrochemically active material composite of claim 1, wherein thesilicon oxide of the formula SiO₂ or the silicon oxide of the formulaSiOx wherein 0<x<2 is chemically bound to the graphene via a chemicalbond.
 16. The electrochemically active material composite of claim 1,wherein the graphene extends from the silicon oxide by a distance ofabout 0.5 nm or less.
 17. The electrochemically active materialcomposite of claim 1, wherein the electrochemically active materialcomposite has specific surface areas of about 14.4 m²/g to about 44.5m²/g, and the composite has a conductivity of about 3.54×10⁻² S/cm toabout 44.5 S/cm.
 18. The electrochemically active material composite ofclaim 1, wherein the composite comprising the particles comprising asilicon oxide of the formula SiO₂ and a silicon oxide of the formulaSiOx wherein 0<x<2; and graphene, is coated on surface of theelectrochemically active material.
 19. The electrochemically activematerial composite of claim 18, wherein the active material includes atleast one selected from lithium nickel cobalt manganese oxide, lithiumnickel cobalt aluminum oxide, lithium iron phosphorous oxide, andlithium manganese oxide.
 20. An electrode comprising theelectrochemically active material composite of claim
 1. 21. Theelectrode of claim 20, wherein the electrode is a cathode or an anode.22. A lithium battery comprising the electrochemically active materialcomposite of claim 1.